JP2014241183A - Laminate for dry etching, method for manufacturing mold, and mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for dry etching, which can prevent crystallization on an interface between a thermally reactive resist layer and an etching layer and has excellent processability by dry etching, and to provide a method for manufacturing a mold, and a mold.SOLUTION: A laminate (10) for dry etching includes a substrate (11), an etching layer (12) disposed on a surface of the substrate (11), and a thermally reactive resist layer (13) directly disposed on a surface of the etching layer (12). The thermally reactive resist layer (13) comprises a thermally reactive resist material and an etching material constituting the etching layer (12), in which a proportion of the etching material is over 15 mol% and 50 mol% or less. The etching layer (12) is subjected to dry etching to form a fine concavo-convex pattern by using a mask obtained by patterning the thermally reactive resist layer (13).

Description

  The present invention relates to a dry etching laminate, a mold manufacturing method, and a mold.

  In recent years, with increasing demands for higher density and higher integration in the fields of semiconductors, optical / magnetic recording, etc., a fine pattern processing technique of several hundred nm to several tens of nm or less is essential. Therefore, in order to realize such fine pattern processing, elemental technologies of each process such as a mask / stepper, exposure, dry etching, resist material and the like are actively studied.

  For example, in the mask / stepper process, a special mask called a phase shift mask is used to provide a phase difference to the light and improve the precision of fine pattern processing by the effect of interference, or between the stepper lens and the wafer. A liquid immersion technique that enables fine pattern processing by filling a liquid and largely refracting light that has passed through a lens has been studied. However, it is very difficult to reduce the manufacturing cost because the former requires an enormous cost for mask development and the latter requires an expensive device.

  On the other hand, many studies have been made on resist materials. Currently, the most common resist material is a photoreactive organic resist (hereinafter also referred to as “photoresist”) that reacts with an exposure light source such as ultraviolet light, electron beam, or X-ray (Patent Document 1, Non-Patent Document). 1).

FIG. 1 is a graph showing the relationship between the spot diameter of laser light and the intensity of laser light. In FIG. 1, the horizontal axis represents the spot diameter (Rs) of the laser beam, and the vertical axis represents the laser beam intensity (E). In the laser light used for the exposure, the intensity (E) of the laser light normally focused by the lens shows a Gaussian distribution with respect to the spot diameter (Rs) as shown in FIG. At this time, the spot diameter (Rs) is defined by 1 / e ² . In general, the reaction of a photoresist is initiated by absorbing energy represented by E = hν (E: energy, h: Planck constant, ν: wavelength). Therefore, the photoreaction does not strongly depend on the intensity of the light, but rather depends on the wavelength of the light, so that almost all the photoreaction occurs in the region irradiated with light (hereinafter referred to as an exposure region). . For this reason, when a photoresist is used, an area corresponding to the spot diameter (Rs) becomes an exposure area.

  The method using a photoresist is a very effective method for forming a fine pattern of about several hundred nm, but the photoreaction proceeds in a region corresponding to the spot diameter. For this reason, in order to form a fine pattern, it is necessary to expose with a spot diameter smaller than the pattern required in principle. Accordingly, a KrF or ArF laser having a short wavelength must be used as the exposure light source. However, since these light source devices are very large and expensive, they are not suitable from the viewpoint of manufacturing cost reduction. Further, when using an exposure light source such as an electron beam or an X-ray, the exposure atmosphere needs to be in a vacuum state. Therefore, it is necessary to use a vacuum chamber, which is limited from the viewpoint of cost and size.

  On the other hand, when an object is irradiated with laser light having a Gaussian distribution as shown in FIG. 1, the temperature of the object also exhibits the same Gaussian distribution as the intensity distribution of the laser light. FIG. 2 is a graph showing the relationship between the laser light exposure region and temperature. In FIG. 2, the horizontal axis indicates the exposure area (Ae), and the vertical axis indicates the temperature (T). At this time, when a resist that reacts at a predetermined temperature or higher (hereinafter, referred to as “thermal reaction type resist”) is used, the reaction proceeds only at a portion that exceeds the predetermined temperature (resist reaction temperature; Tr) as shown in FIG. Therefore, it becomes possible to expose a region (Ae) smaller than the spot diameter (Rs). That is, a pattern finer than the spot diameter (Rs) can be formed without shortening the wavelength of the exposure light source, so that the influence of the wavelength of the exposure light source can be reduced by using a heat-reactive resist. Can do.

In the field of optical recording, WO _X , MoO _X , other chalcogenide glasses (Ag-As-S series), etc. are used as thermal reaction type resists, and a technique for forming fine patterns by exposure with a semiconductor laser or 476 nm laser is proposed. (See Patent Document 2 and Non-Patent Document 2). These optical disks used in the field of optical recording are generic names of media that read information recorded on fine irregularities provided on the disk surface by irradiating a disk coated with a resist material with a laser. In an optical disc, the smaller the recording unit interval called track pitch, the higher the recording density and the larger the data capacity that can be recorded for each area. For this reason, in order to improve the recording density, research on processing technology for fine concavo-convex patterns using a resist material has been conducted.

  Hitherto, it has been proposed to form silicon oxide in the lower layer of a resist layer to suppress the formation of an interface layer and improve resist characteristics (see Patent Document 3 and Patent Document 4).

  In particular, in Patent Document 4, in an inorganic resist pattern including a base material and an inorganic resist layer made of an amorphous metal oxide, a base layer is formed on the base material as an accumulation layer, and the base layer and the inorganic resist layer are formed. It is disclosed that an intermediate layer (hereinafter referred to as a crystallization suppressing layer) for suppressing crystallization at the interface of the inorganic resist layer is provided between the resist layer and the resist layer. As the crystallization suppressing layer, it is disclosed that when the underlayer is amorphous silicon, silicon oxide is used, or a mixture of a material constituting the underlayer and a material constituting the inorganic resist layer is used.

JP 2007-144959 A Japanese Patent Laying-Open No. 2005-203552 Japanese Patent Laid-Open No. 11-115315 JP 2008-47251 A

Published by Information Organization Co., Ltd. “Latest Resist Materials” 59-P. 76 SPIE Vol. 3424 (1998) p. 20

  However, in the case where a fine pattern is formed on the etching layer to be processed using the above-described thermal reaction type resist as a mask, it is necessary to expose the surface of the etching layer inside the opening of the mask. For this reason, when a crystallization suppression layer is provided between the thermal reaction type resist and the etching layer, the crystallization suppression layer needs to be dry-etched. Since the technique disclosed in Patent Document 4 relates to the formation of a fine pattern in a method of manufacturing an optical disc master (stamper), there is no mention of dry etching the crystallization suppression layer.

  Moreover, it is extremely difficult to apply the crystallization suppressing layer disclosed in Patent Document 4, and it is not practical. That is, when silicon oxide or a mixture of the material constituting the underlayer and the material constituting the inorganic resist layer is used for the crystallization suppression layer, the dry etching resistance of the crystallization suppression layer is increased and the crystallization suppression is suppressed. The layer cannot be dry-etched or is non-uniformly dry-etched, resulting in poor workability by dry etching. Therefore, the crystallization suppressing layer is effective for preventing crystallization at the interface between the inorganic resist layer and the etching layer, but is not suitable for forming a uniform pattern by dry etching using the inorganic resist layer as a mask.

  The present invention has been made in view of the above-described problems, and can prevent crystallization at the interface between the heat-reactive resist layer and the object to be processed and is excellent in workability by dry etching. It aims at providing a laminated body, a manufacturing method of a mold, and a mold.

  As a result of intensive research in order to solve the above problems, the present inventors have added an etching material constituting the object to be processed to the thermal reaction resist at a predetermined ratio, so that the thermal reaction resist layer and the object to be processed are added. It has been found that crystallization at the interface of the processed body can be prevented and a uniform fine uneven pattern can be formed on the processed body by dry etching, and the present invention has been made. That is, the present invention is as follows.

  The dry etching laminate according to the present invention includes a target object and a heat-reactive resist layer provided directly on the surface of the target object, and the heat-reactive resist layer is a heat-reactive resist layer. It contains a resist material and an etching material constituting the object to be processed, and a ratio of the etching material is more than 15 mol% and 50 mol% or less.

  This configuration reduces the difference in interfacial energy between the object to be processed and the thermal reaction type resist layer, suppresses crystallization at the interface between the heat reaction type resist layer and the object to be processed, and prevents the formation of the interface layer. A uniform mask can be obtained, and a uniform fine uneven pattern can be formed on the object by dry etching.

  In the laminate for dry etching according to the present invention, the thermal reaction type resist material is made of a material having a boiling point of main fluoride of 250 ° C. or higher, and the etching material is made of a material having a boiling point of main fluoride of less than 250 ° C. It is preferable.

  In the dry etching laminate according to the present invention, it is preferable that the thermal reaction type resist material and the etching material are not compatible with each other at a pattern forming temperature.

  In the dry etching laminate according to the present invention, it is preferable that the thermal reaction type resist layer has a thickness of 5 nm to 1 μm.

  In the laminate for dry etching according to the present invention, the object to be processed is preferably an etching layer provided on the surface of the substrate.

  In the laminate for dry etching according to the present invention, the object to be processed is preferably a base material.

  In the dry etching laminate according to the present invention, it is preferable that the substrate has a flat plate shape, a cylindrical shape, or a lens shape.

  In the mold manufacturing method according to the present invention, a thermal reaction type resist material and an etching material constituting the object to be processed are contained on the object to be processed, and the ratio of the etching material is more than 15 mol% and not more than 50 mol%. A step of directly forming a heat-reactive resist layer; a step of exposing the heat-reactive resist layer; a step of developing the heat-reactive resist layer to form a mask; and the object to be processed through the mask And a step of dry-etching and obtaining a mold by removing the thermal reaction type resist layer.

  This configuration reduces the difference in interfacial energy between the object to be processed and the thermal reaction type resist layer, suppresses crystallization at the interface between the heat reaction type resist layer and the object to be processed, and prevents the formation of the interface layer. A mask having a uniform fine uneven pattern can be manufactured using dry etching.

  In the mold manufacturing method according to the present invention, the thermal reaction type resist layer is preferably provided by a sputtering method, a vapor deposition method or a CVD method.

  In the mold manufacturing method according to the present invention, the object to be processed is preferably an etching layer provided on the surface of the substrate.

  In the mold manufacturing method according to the present invention, the etching layer is preferably provided by a sputtering method, a vapor deposition method or a CVD method.

  In the mold manufacturing method according to the present invention, the object to be processed is preferably a base material.

  In the mold manufacturing method according to the present invention, it is preferable that the substrate has a flat plate shape, a cylindrical shape, or a lens shape.

  In the mold manufacturing method according to the present invention, it is preferable to use a semiconductor laser for the exposure of the thermal reaction type resist layer.

  The mold according to the present invention is manufactured by the above-described mold manufacturing method.

  The mold according to the present invention preferably has a fine concavo-convex pattern having a pitch of 1 nm or more and 1 μm or less.

  According to the present invention, the above configuration can prevent an interface layer (crystallization of the thermal reaction resist, etc.) at the interface between the thermal reaction resist layer and the object to be processed, and is excellent in workability by dry etching. A dry etching laminate, a mold manufacturing method, and a mold can be provided.

It is a graph which shows the relationship between the spot diameter of a laser beam, and laser beam intensity. It is a graph which shows the relationship between the exposure area | region of a laser beam, and temperature. It is a cross-sectional schematic diagram which shows the laminated body for dry etching which concerns on this Embodiment. It is a graph which shows the relationship between the boiling point of main fluoride, and an etching rate. It is a cross-sectional schematic diagram which shows each process of the manufacturing method of the mold which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows each process of the manufacturing method of the mold which concerns on this Embodiment.

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

(Overview)
An outline of the dry etching laminated body according to the present embodiment will be described. As described above, in the heat-reactive resist, some thermal alteration occurs in the exposed region (Ae in FIG. 2) whose temperature has been increased by exposure, and there is an exposed region in which thermal alteration has occurred and an unexposed region that has not undergone alteration. It is formed. For this reason, by passing through a development process, it becomes possible to form a fine concavo-convex pattern corresponding to an exposure pattern having a wavelength equal to or less than that of a laser beam or the like used for exposure. When the heat-reactive resist is an ablation type that evaporates or sublimates, the development process may be performed as necessary.

  However, in the formation of a fine concavo-convex pattern using a heat-reactive resist, an interface layer is generated at the interface between the heat-reactive resist layer composed of the heat-reactive resist material and the etching layer. The interface layer is different in solubility in the developer from the heat-reactive resist layer, and it becomes difficult to dissolve a part of the interface layer during development, so the mask becomes non-uniform, resulting in a fine uneven pattern on the object to be processed. The problem that it cannot form uniformly arises.

  The present inventors have found that the formation of the interface layer is due to the difference in the interface energy between the heat-reactive resist material and the etching layer, and have further conducted extensive research. As a result, the present invention has been completed.

  The laminate for dry etching according to the present embodiment includes a base material, an etching layer provided on the surface of the base material, and a heat-reactive resist layer provided directly on the surface of the etching layer, The heat-reactive resist layer contains a heat-reactive resist material and an etching material constituting the object to be processed, and the ratio of the etching material is more than 15 mol% and 50 mol% or less.

  The dry etching laminate according to the present embodiment reduces the difference in interfacial energy between the etching layer and the heat-reactive resist layer with the above structure, and the heat-reactive resist at the interface between the heat-reactive resist layer and the object to be processed. The crystallization of the material can be suppressed and the formation of the interface layer can be prevented. As a result, the development characteristics of the heat-reactive resist layer are improved, and a uniform mask can be obtained. A uniform fine uneven pattern can be formed on the etching layer by dry etching using this mask.

(Details)
FIG. 3 is a schematic cross-sectional view showing the dry etching laminate according to the present embodiment. As shown in FIG. 3, the dry etching laminate 10 includes a base material 11, an etching layer 12 provided on the base material 11, a thermal reaction resist layer 13 provided directly on the etching layer 12, At least.

  As shown in FIG. 3, the etching layer 12 is provided on the base material 11 to be processed, but the base material 11 itself may be used as the processing target and may also serve as the etching layer 12. In this case, the heat-reactive resist layer 13 can be directly provided on the substrate 11.

(Thermal reaction type resist layer)
In the dry etching laminated body 10 according to the present embodiment, the thermal reaction type resist layer 13 contains a thermal reaction type resist material and an etching material constituting the etching layer 12, and the ratio of the etching material is more than 15 mol% and 50 mol. % Or less. By adding more than 15 mol% of the etching material to the heat-reactive resist material, the formation of the interface layer can be suppressed, and when it is 50 mol% or less, the resist characteristics can be exhibited.

  Here, specifically, the resist characteristics are excellent in the ability to form a fine concavo-convex pattern, have excellent dry etching resistance, that is, excellent in mask performance, and in addition, have characteristics that can very well suppress the formation of the interface layer. That means.

  The ratio of the etching material is more preferably more than 15 mol% and not more than 40 mol%, more preferably more than 15 mol% and not more than 30 mol%, and most preferably not less than 18 mol% and not more than 30 mol%.

  The preferable range of the ratio of the etching material can be appropriately selected depending on the combination of the thermal reaction type resist material and the etching material. However, if the amount of the etching material added is too large, the dry etching resistance of the thermal reaction type resist layer 13 is lowered. Since there exists a tendency, it is preferable to select an addition ratio in the said range. When the ratio of the etching material is 18 mol% or more and 30 mol% or less, the resist material is excellent in resist characteristics, that is, a fine uneven pattern forming ability, and is excellent in dry etching resistance, that is, mask performance, and in addition, the interface is very good. It can also have the characteristic that formation of a layer can be controlled.

(Fluoride)
In the dry etching laminate 10 according to the present embodiment, the heat-reactive resist material is made of a material having a boiling point of main fluoride of 250 ° C. or higher, and the etching material is a material having a boiling point of main fluoride of less than 250 ° C. Preferably it consists of. The etching layer 12 is patterned by dry etching using the thermal reaction type resist layer 13 partially opened through exposure and development processes as a mask, and the mask pattern is transferred. For this reason, it is preferable that the etching material which comprises the etching layer 12 is easy to dry-etch. At that time, the dry etching resistance of the etching material is an important material selection index. In the pamphlet of International Publication No. 2010/044400, the present inventors disclose the relationship between the boiling point of fluoride and the resistance to dry etching using a fluorocarbon gas. According to the present inventors, if the boiling point of fluoride is low, dry etching resistance using chlorofluorocarbon gas is low, so that dry etching is easy. In view of the above, the etching material is preferably made of a material having a boiling point of the main fluoride of less than 250 ° C.

  On the other hand, since the thermal reaction type resist layer 13 functions as a mask at the time of dry etching, it is preferable that it is difficult to be dry etched. Therefore, as described above, the heat-reactive resist material is preferably made of a material having a fluoride boiling point of 250 ° C. or higher.

In addition, the boiling point of the main fluoride means the boiling point of the main valence fluoride of metal (= the boiling point of the main fluoride) when the element forms a polyvalent fluoride. For example, when tungsten is taken as an example, tungsten can have a valence of 2, 4, 5, or 6. For this reason, WF ₂ , WF ₄ , WF ₅ , and WF ₆ can be formed as the fluoride of tungsten. However, since the main valence of tungsten is hexavalent, the main fluoride of tungsten is WF _6. the points, the boiling point of the primary fluoride refers to a boiling point of WF _6.

  The boiling point of the fluoride of the element constituting the heat-reactive resist material is 250 ° C. or higher, preferably 500 ° C. or higher, more preferably 700 ° C. or higher, further preferably 800 ° C. or higher, and most preferably 950 ° C. or higher. . As the boiling point of fluoride increases, the resistance to dry etching using a fluorocarbon gas increases.

  Tables 1 and 2 below show typical examples of the boiling points of the fluorides of elements constituting the heat-reactive resist material used in the dry etching laminate 10 according to the present embodiment.

Further, FIG. 4 shows the relationship between the boiling points of the fluorides of various metals disclosed in this specification and the dry etching rate by CF ₄ gas. FIG. 4 is a graph showing the relationship between the boiling point of the main fluoride and the etching rate.

  As suggested by FIG. 4, the heat-reactive resist material can have high dry etching resistance by being composed of an element having a boiling point of fluoride of 250 ° C. or higher. That is, when the boiling point of fluoride is below 250 ° C., the dry etching rate increases exponentially. Here, FIG. 4 shows the dry etching rate of a single metal, but the oxides, nitrides, carbides, carbonates, and selenides also greatly affect the dry etching rate of the metal contained in each compound. , The trend is the same.

  Specifically, materials whose boiling point of the main fluoride used as an etching material is less than 250 ° C. are boron, carbon, silicon, phosphorus, sulfur, vanadium, germanium, selenium, niobium, molybdenum, tellurium, tantalum, tungsten, rhenium. , Iridium, platinum and the like. Among these, the main material constituting the etching layer 12 is, for example, silicon, vanadium, germanium, niobium, molybdenum, tellurium, tantalum and tungsten, and a group consisting of these oxides, nitrides and oxynitrides. And at least one selected from. Among them, a material mainly composed of oxide, nitride, or oxynitride is preferable, and more preferably at least one oxide, nitride, or oxynitride selected from the group consisting of silicon, niobium, tellurium, and tantalum. Most preferably, from the viewpoint of the boiling point of the main fluoride and the reaction with the heat-reactive resist material, the oxide, nitride or oxynitride of silicon, tantalum or a mixture thereof is most preferable. It is a material mainly composed of any compound. Of the oxides, nitrides, and oxynitrides, oxides are most preferable from the viewpoints of manufacturing, reaction with the heat-reactive resist material, and heat stability. From the above, oxides of silicon, tantalum, or a mixture thereof are most preferable.

  Next, the thermal reaction type resist material will be described. Since the thermal reaction type resist material used for the dry etching laminate 10 according to the present embodiment acts as a mask pattern in dry etching, as described above, a material having a boiling point of fluoride of 250 ° C. or higher is used. Preferably, for example, the following heat-reactive resist can be mentioned.

  In the present embodiment, as the heat-reactive resist material, incomplete oxide, decomposable oxide, decomposable nitride, decomposable carbide, decomposable carbonate, decomposable sulfide, decomposable selenide, meltability It is preferable to contain any of a composite metal material, a phase change composite metal material, or an oxidizable composite metal material.

  The incomplete oxide is preferably an incomplete oxide of an element selected from the group consisting of transition metals and Group XII to XV elements. Incomplete oxides include Ti, Cr, Mn, Fe, Co, Ni, Cu, Zr, Rh, Ag, Hf, Au, Al, Zn, Ga, In, Sn, Sb, Pb, and Bi. Preferably an incomplete oxide of an element selected from the group, an incomplete oxide of an element selected from the group consisting of Ti, Cr, Mn, Co, Cu, Ag, Au, Sn, Pb and Bi More preferably it is.

Decomposable oxides include CuO, Co ₃ O ₄ , MnO ₂ , Mn ₂ O ₃ , CrO ₃ , Cr ₅ O ₁₂ , PbO ₂ , Pb ₃ O ₄ , Rh ₂ O ₃ , RuO ₂ , MgO ₂ , CaO. ₂ , BaO ₂ or ZnO ₂ is preferred. As the decomposable _{oxide, CuO, Co 3 O 4,} MnO 2, Mn 2 O 3, CrO 3, Cr 5 O 12, PbO 2, Pb 3 O 4, MgO 2, CaO 2, BaO 2 or ZnO ₂ is more preferable. Further, the decomposable oxide is more preferably CuO, Co ₃ O ₄ , MnO ₂ , Mn ₂ O ₃ , CrO ₃ , Pb ₃ O ₄ , BaO ₂ or CaO.

The decomposable nitride is preferably Zn ₃ N ₂ , CrN, Cu ₃ N, Fe ₂ N, or Mg ₃ N ₂ . The decomposable carbide is more preferably NdC ₂ or Al ₄ C ₃ .

The decomposable carbonate is preferably MgCO ₃ , CaCO ₃ , SrCO ₃ , BaCO ₃ , ZnCO ₃ , CdCO ₃ , Ag ₂ CO ₃ , PbCO ₃ or NiCO ₃ . The decomposable carbonate is more preferably MgCO ₃ , CaCO ₃ , SrCO ₃ or BaCO ₃ .

Decomposable sulfides include CuS, Ni ₃ S ₄ , FeS, FeS ₂ , Fe ₂ S ₃ , SnS ₂ , HfS ₂ , TiS ₂ , Rh ₂ S ₃ , RuS ₂ , Bi ₂ S ₃ , Cr ₂ S _3. GaS, BaS ₃ , MnS ₂ or Nd ₂ S ₃ is preferred. The decomposable sulfide is more preferably CuS, FeS ₂ , SnS ₂ or HfS ₂ , and further preferably FeS ₂ or SnS ₂ .

The decomposable selenide is preferably CuSe, Bi ₂ Se ₃ , FeSe or GaSe. The decomposable selenide is more preferably CuSe.

  Examples of the meltable composite metal material, phase change composite metal material or oxidizable composite metal material include Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, Cr, Mn, Fe, Co, Ni, Cu , Ag, Zn, Al, Ga, In, Sn, Pb, Sb and Bi, and a metal group (α) and V, Mo, W, Ge, Se, Nb, Ta and Te. It is preferable that two kinds of metals selected from the group are contained, and at least one of the metals is selected from the metal group (α).

  Moreover, as a meltable composite metal material, a phase change composite metal material or an oxidizable composite metal material, Mg, Ti, Zr, Cr, Mn, Fe, Co, Ni, Cu, Ag, Zn, Al, Ga, In , Pb, Sb and Bi containing two types of metals selected from the group consisting of metal (γ) and the group consisting of metal group consisting of V, Mo, W, Ge and Te (δ), More preferably, at least one kind is selected from the metal group (γ).

  Further, as a meltable composite metal material, a phase change composite metal material or an oxidizable composite metal material, In—Sb, Sn—Sb, Cr—Sb, Ga—Sb, In—Sn, Ni—Sn, Al—Sn can be used. Bi-Sn, Sn-Pb, Ni-Bi, Zn-Sb, Ni-Cr, Ni-Nb, Al-Ni, Cu-Zr, Ag-Zn, Ge-Sb, Sb-Te, Bi-Te, Ni It is more preferable to contain any of the combinations of metal species represented by -W, Zn-Te, Pb-Te, Cr-Mo and Cu-V.

In addition, examples of the meltable composite metal material, the phase change composite metal material, and the oxidizing composite metal material include In ₅ Sb ₉₅ , In ₃₂ Sb ₆₈ , In ₆₈ Sb ₃₂ , In ₁ Sb ₉₉ , Sn ₅₀ Sb ₅₀ , and Cr _{50. Sb 50, Ga 50 Sb 50,} Ga 40 Sb 60, Ga 30 Sb 70, Ga 20 Sb 80, Ga 12 Sb 88, Ga 10 Sb 90, In 47 Sn 53, In 53 Sn 47, Ni 80.7 Sn 19. ₃ , Al _2.2 Sn _97.8 , Bi ₄₃ Sn ₅₇ , Sn ₂₆ Pb ₇₄ , Sn ₂₅ Pb ₇₅ , Sn ₇₄ Pb ₂₆ , Ni ₅₀ Bi ₅₀ , Ni ₄₀ Bi ₆₀ , Ni ₆₀ Bi ₄₀ , Ni ₇₀ Bi ₃₀ , Ni ₈₀ Bi ₂₀ , Ni ₉₀ Bi ₁₀ , Zn ₃₂ Sb ₆₈ , Ni ₅₀ Cr ₅₀ , Ni _83.8 Nb _16.2 , Ni _59.8 Nb _40.2 , Al _97.3 Ni _2.7 , Cu _90.6 Zr _9.4 , Ag ₇₀ Zn ₃₀ , Ge ₁₀ Sb ₉₀ , Ge ₂₀ Sb _{80 , Ge 30 Sb 70, Ge 50} Sb 50, Bi 90 Te 10, Bi 97 Te 3, Ni 81 W 19, Zn 50 Te 50, Pb 50 Te 50, Cr 85 Mo 15, Sb 40 Te 60, Bi 10 Te 90 Cu _8.6 V _91.4 , Cu _13.6 V _86.4 or Cu _18.6 V _81.4 is particularly preferable. Furthermore, fusible composite metal material, the phase change composite metal material or oxidizing composite metal _{material, Sb 40 Te 60, Bi 10} Te 90, Cu 8.6 V 91.4, Cu 13.6 V 86.4 Or Cu _18.6 V _81.4 is most preferable.

As the heat-reactive resist material according to the present embodiment, any of incomplete oxides of Cr, Ti, Sn, or Pb, Mn ₂ O ₃ , CuO, Co ₃ O ₄ , Pb ₃ O ₄ , BaO ₂ , Any of CaCO ₃ , FeS ₂ or SnS ₂ is preferred. From the viewpoint of forming a finer pattern, copper oxide (CuO), chromium oxide (incomplete oxide of Cr), tin oxide (incomplete oxide of Sn), cobalt oxide (Co ₃ O ₄ ) or is preferably manganese oxide _(Mn 2 _{O 3)} is a material mainly. Further, from the viewpoint of reactivity with the etching material, a material mainly composed of copper oxide (CuO) or chromium oxide (incomplete oxide of Cr) is preferable. Most preferred is copper oxide (CuO).

(Etching layer)
In the dry etching laminate 10 according to the present embodiment, the thermal reaction type resist layer 13 and the etching layer 12 are exposed in a state of being in contact with each other at the interface. The heat-reactive resist material constituting the heat-reactive resist layer 13 is a material that induces thermal alteration by being heated by exposure and increasing in temperature. In order to form a uniform pattern of the heat-reactive resist material, as an etching material constituting the etching layer 12, the temperature at which the heat-reactive resist material is thermally altered as much as possible, that is, when the heat-reactive resist layer 13 is patterned. A material that is incompatible with the heat-reactive resist material at the pattern formation temperature is preferable. An etching material that is incompatible with the heat-reactive resist material at the pattern formation temperature can be selected with reference to, for example, a phase diagram.

  In the present embodiment, the thickness of the etching layer 12 can be adjusted according to a desired etching depth. For example, it is preferably in the range of 5 nm to 100 μm, more preferably 50 nm to 5 μm.

  On the other hand, the film thickness of the heat-reactive resist layer 13 is preferably in the range of 5 nm to 1 μm. When the film thickness of the heat-reactive resist layer 13 is too thin, the heat-reactive resist layer 13 cannot be sufficiently absorbed by exposure, so that the temperature is not raised to a necessary temperature, and patterning by exposure cannot be performed well. If the thickness of the thermal reaction type resist layer 13 is too thick, a temperature distribution is formed in the thickness direction, and regions and states that are thermally altered in the thermal reaction type resist layer 13 are different, so that accurate patterning cannot be performed. From the above, the thickness of the thermal reaction type resist layer 13 is preferably 5 nm or more and 1 μm or less, more preferably 5 nm or more and 500 nm or less, particularly preferably 5 nm or more and 100 nm or less, and more preferably 10 nm or more. Most preferably, it is 100 nm or less.

(Base material)
In the dry etching laminate 10 according to the present embodiment, the material of the base material 11 is not particularly limited, but it is possible to use a metal, glass, or the like that is rich in workability. Specifically, aluminum, copper, titanium, SUS, silicon, glass, quartz, or those plated with chromium can be used.

  Further, the base material 11 may also serve as the etching layer 12. At this time, the material constituting the substrate 11 is not particularly limited as long as the boiling point of the main fluoride is less than 250 ° C., but, for example, silicon, germanium, molybdenum, tellurium, tantalum, tungsten, carbon, and oxides thereof And nitride, more preferably silicon and its oxides and nitrides, more preferably silicon oxide, from the viewpoint of availability, stability, dry etching resistance, surface smoothness, etc. Most preferred is quartz.

  In the dry etching laminate 10 according to the present embodiment, examples of the shape of the substrate 11 include a flat plate shape, a cylindrical shape (a sleeve, a roll, and a drum), and a lens shape. By using the base material 11 of these shapes, the shape of the base material 11 can be used as it is as the shape of the mold.

  The shape of the substrate 11 can be selected as appropriate according to the shape of the mold to be produced. Many molds used for optical disc masters, nanoimprints, and the like are small and flat, and can be transferred by a simple device. When transferring to a large area with a plate-shaped mold, it is necessary to produce a large mold, but it is necessary to apply a uniform pattern to the entire surface of the large mold, to apply a uniform pressing pressure to the entire mold surface during transfer, There are problems such as clean release of the mold. On the other hand, a sleeve (cylindrical) mold can be manufactured by using a sleeve base material, and a large-area pattern can be easily manufactured by transferring with the sleeve-shaped mold. Furthermore, the lens-shaped mold can be used as a mold by directly imparting an antireflection structure or the like to the lens-shaped substrate, and the lens-shaped substrate can be used as a final product as it is.

(Mold manufacturing method)
Next, a method for manufacturing the mold according to the present embodiment will be described. 5 and 6 are schematic cross-sectional views showing the respective steps of the mold manufacturing method according to the present embodiment.

  In the mold manufacturing method according to the present embodiment, first, (1) as shown in FIG. 5A, an etching layer 12 made of an etching material is formed on a base material 11.

  Next, (2) as shown in FIG. 5B, a thermal reaction type resist layer containing a thermal reaction type resist material and an etching material on the etching layer 12, and the ratio of the etching material is more than 15 mol% and not more than 50 mol%. 13 is formed directly. Thus, the dry etching laminate 10 according to the present embodiment is obtained.

  Next, (3) the heat-reactive resist layer 13 is partially exposed. As a result, as shown in FIG. 5C, an exposed region 13 a and an unexposed region 13 b are generated in the thermal reaction type resist layer 13.

  (4) The thermal reaction type resist layer 13 is developed to form a mask 13c as shown in FIG. 6A. That is, the exposure region 13a shown in FIG. 5C is dissolved with a developer and removed.

  (5) The etching layer 12 is dry-etched through the mask 13c to form a recess 12a corresponding to the opening of the mask 13c in the etching layer 12 as shown in FIG. 6B.

  (6) The remaining thermal reaction type resist layer 13 is removed, and an etching layer 12 on which a fine concavo-convex pattern including concave portions 12a and convex portions 12b as shown in FIG. 6C is formed, and a substrate 11 are provided. A mold 14 is obtained.

  When the base material 11 also serves as the etching layer 12, the thermal reaction type resist layer 13 is directly formed on the base material 11 in the steps (1) and (2). In step (5), the substrate 11 is dry-etched in place of the etching layer 12.

  Further, in the step (1) and the step (2), the etching layer 12 and the thermal reaction type resist layer 13 can be formed by using a sputtering method, a vapor deposition method, or a CVD method. Since these layers can be processed with a fine pattern on the order of several tens of nanometers, depending on the fine pattern size, the film thickness distribution of the heat-reactive resist layer 13 during film formation and the unevenness of the surface can have a significant effect. Can be considered. Therefore, in order to reduce these effects as much as possible, a thermal reaction type resist layer is formed by sputtering, vapor deposition or CVD rather than coating or spraying, which is somewhat difficult to control film thickness uniformity. It is preferable to do. Among these, the sputtering method is particularly preferable from the viewpoints of composition adjustment, film thickness uniformity, film formation rate, and the like.

  In step (3), the heat source is not particularly limited as long as it can heat the heat-reactive resist layer 13 and can achieve a desired pattern shape, but a laser capable of easily forming a pattern is preferable. As a laser used for exposure of the heat-reactive resist layer 13, for example, an excimer laser such as a KrF laser or an ArF laser, a semiconductor laser, an electron beam, and an X-ray can be used. Excimer lasers are very large and expensive, and electron beams and X-rays require the use of a vacuum chamber. Therefore, there are considerable limitations in terms of cost and size. Therefore, it is preferable to use a semiconductor laser that can be made very compact and inexpensive. In general, it has been possible to form a fine pattern by shortening the wavelength of an exposure light source using an electron beam, excimer laser, or the like. However, the dry etching laminate 10 according to the present embodiment is sufficient even with a semiconductor laser. It is possible to form a fine pattern.

  For the development of the heat-reactive resist layer 13 in the step (4), for example, an acid solution, an alkali solution, a complexing agent, and an organic solvent can be used alone or in combination in a timely manner.

  As the acid solution, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, hydrofluoric acid, ammonium nitrate, or the like can be used. As the alkaline solution, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, TMAH (tetramethylammonium hydroxide) or the like can be used. As the complexing agent, a solution of oxalic acid, ethylenediaminetetraacetic acid and its salt, glycine or the like can be used alone or as a mixed solution. Further, a potential adjusting agent such as hydrogen peroxide or manganese peroxide may be added to the developer. Further, the developing property may be improved by adding a surfactant or the like to the developer. Further, after developing with an acid developer, development is performed with an alkali developer to achieve a desired development, or after developing with an alkali developer, development with an acid developer is performed to achieve the desired development. A wide range of development may be performed. Depending on the thermal reaction type resist to be selected, development may not be necessary.

In the step (5), the apparatus used for dry etching is not particularly limited as long as it can introduce a chlorofluorocarbon gas in a reduced-pressure atmosphere, can form plasma, and can perform an etching process. A dry etching apparatus, an RIE apparatus, and an ICP apparatus can be used. The gas type, time, power, etc. for performing the dry etching treatment can be appropriately determined depending on the type of the thermal reaction type resist layer 13, the type of the etching layer 12 or the substrate 11, the thickness, the etching rate, and the like. Examples of the etching gas include fluorine-based gases such as CF ₄ and SF ₆ , and these may be used alone or in combination with a plurality of gases. Further, a mixture in which the above-described fluorine-based gas and a gas such as O ₂ , H ₂ , Ar, N ₂ , CO, HBr, NF ₃ , HCl, HI, BBr ₃ , BCl ₃ , Cl ₂ , and SiCl ₄ are mixed. The gas is also within the range of fluorine-based gas.

  In the mold 14 manufactured by the above-described method, the pitch of the concavo-convex structure (pitch between adjacent convex portions) has a fine concavo-convex pattern in the range of 1 nm or more and 1 μm or less. In addition, the pitch here does not necessarily need to be the pitch between adjacent convex parts of a concavo-convex structure, and may be the pitch between adjacent concave parts. Further, the shape of the concavo-convex structure is not particularly limited, and examples thereof include a line and space shape, a dot shape, or a long hole shape in a plan view, and these shapes may be mixed. Examples of the cross-sectional structure of the concavo-convex structure include a triangular shape, a rectangular shape, a dome shape, and a lens shape.

  According to the mold manufacturing method according to the present embodiment described above, the etching material constituting the etching layer 12 is added to the thermal reaction type resist material constituting the thermal reaction type resist layer 13 at a predetermined ratio. The difference in interface energy between the etching layer 12 and the thermal reaction type resist layer 13 is reduced, crystallization can be suppressed at the interface between the thermal reaction type resist layer 13 and the etching layer 12, and the formation of the interface layer can be prevented. 13c is obtained, and a mold 14 having a uniform fine uneven pattern can be manufactured by dry etching.

  Examples performed to confirm the effects of the present invention will be described below. In addition, this invention is not limited at all by the following examples and comparative examples.

Example 1
Three silicon substrates of 50 mmφ were prepared as base materials. On these three silicon substrates, SiO ₂ was sputtered as an etching layer under the conditions of an electric power of 100 W and an Ar gas pressure of 0.1 Pa to form 300 nm thick etching layers, respectively. Next, CuO-18 mol% SiO ₂ , CuO-25 mol% SiO _2, and CuO-30 mol% SiO ₂ were mixed on the etching layers formed on the three silicon substrates, respectively, with a power of 100 W and a mixed gas of Ar and O ₂ . Sputtering was performed under the condition of a pressure of 0.1 Pa to form three types of heat-reactive resist layers having a thickness of 20 nm. In this manner, three types of laminates composed of a substrate, an etching layer, and a heat-reactive resist layer were produced.

Next, the heat-reactive resist layer of the laminate was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 1mW to 25mW
Feed pitch: 120 nm to 1000 nm

  Various shapes and patterns can be formed by modulating the intensity of the laser during exposure. In this embodiment, an isolated circle (opening diameter 180 nm) is used as the pattern in order to confirm the uniformity of the fine pattern. Formed. As a pattern shape to be formed, a continuous groove shape, an isolated elliptical shape, or the like can be selected depending on a desired application.

  Next, the heat-reactive resist layer of the above laminate was developed with a 0.3% glycine aqueous solution to form a pattern having a circular opening. SEM measurement was performed on the openings of the formed pattern. As a result, in each thermal reaction type resist layer, the opening diameter of the opening of the pattern was 180 nm, and insoluble matter derived from the interface layer was not confirmed at the bottom (concave) of the opening.

Next, using this pattern as a mask, the etching layer was removed by dry etching using SF ₆ gas under the conditions of power 300 W and gas pressure 5 Pa, and the mask was further removed to produce a mold. When the obtained mold was observed by SEM, it was found that a pattern having a uniform opening in the etching layer was obtained.

(Example 2)
A laminated body was produced under the same conditions as in Example 1 except that the composition of the thermal reaction type resist layer was changed to CrO-18 mol% SiO ₂ , CrO-25 mol% SiO ₂ , and CrO-30 mol% SiO _2. did.

  Subsequently, the heat-reactive resist layer of the above-mentioned laminate was exposed under the same conditions as in Example 1. Thereafter, the heat-reactive resist layer was developed with an alkaline developer to form a pattern having a circular opening. SEM measurement was performed on the openings of the formed pattern. As a result, in each thermal reaction type resist layer, the opening diameter of the opening of the pattern was 180 nm, and insoluble matter derived from the interface layer was not confirmed at the bottom of the opening (recess).

Next, using this pattern as a mask, the etching layer was removed by dry etching using CF ₄ gas under conditions of power of 300 W and gas pressure of 5 Pa, and the mask was removed to produce a mold. When the obtained mold was observed by SEM, it was found that a pattern having a uniform opening was obtained.

Example 3
A 80 mmφ × 400 mm sleeve-shaped quartz substrate (SiO ₂ ) was prepared as a substrate. On this quartz substrate, CuO-20% SiO ₂ is sputtered under the conditions of power 1000 W and mixed gas pressure of Ar and O ₂ of 0.1 Pa to directly form a thermal reaction type resist layer having a thickness of 25 nm. Was made.

Next, the heat-reactive resist layer of the laminate was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 1mW to 25mW
Feed pitch: 120 nm to 350 nm
Rotation speed: 210rpm-1670rpm

  In this example, an isolated circle (opening diameter: 170 nm) was formed as a pattern in order to confirm the uniformity of the fine pattern.

  Next, the heat-reactive resist layer of the laminate was developed with a 0.3% glycine aqueous solution to form a pattern having a circular opening. A UV curable resin was applied on the heat-reactive resist layer, and UV cured to obtain a UV-cured film to which the pattern of the heat-reactive resist layer was transferred. This UV cured film was subjected to SEM measurement. As a result, the opening diameter of the opening portion of the pattern transferred to the UV cured film was 170 nm, the pattern height was 25 nm, and insoluble matter derived from the interface layer was not confirmed at the bottom portion (concave portion) of the opening portion of the substrate.

Next, using the pattern formed in this heat-reactive resist layer as a mask, the quartz substrate is dry-etched using CF ₄ gas under conditions of power 1000 W and gas pressure 5 Pa, and the remaining mask is removed. Thus, a mold was produced. A UV curable resin was applied to the surface of the obtained mold, and UV cured to obtain a UV curable film to which the pattern of the mold was transferred. When this UV cured film was observed by SEM, it was found that a uniform pattern was obtained.

(Comparative Example 1)
Except for changing the composition of the thermal reaction type resist layer _CuO-13mol% SiO 2, the CuO-60mol% SiO ₂ is in the same condition as in Example 1 to prepare a laminate.

Next, the heat-reactive resist layer of the laminate was exposed under the same conditions as in Example 1. Thereafter, the heat-reactive resist layer was developed with a 0.3% glycine aqueous solution. As a result, the laminated body using CuO-13 mol% SiO ₂ as a resist obtained a pattern having a circular opening. The SEM measurement was performed about the opening part of the obtained pattern. As a result, the opening diameter of the opening of the pattern of the thermal reaction type resist layer was 180 nm, and insoluble matter derived from the interface layer was confirmed at the bottom of the opening (recess). On the other hand, a laminate using CuO-60 mol% SiO ₂ as a resist has a large amount of added SiO ₂ , so that a pattern cannot be formed due to insufficient exposure power.

(Comparative Example 2)
A laminate was produced under the same conditions as in Example 1 except that the composition of the heat-reactive resist layer was changed to CuO-60 mol% SiO ₂ and the film thickness was changed to 100 nm.

  Next, the heat-reactive resist layer of the laminate was exposed under the same conditions as in Example 1. Thereafter, the heat-reactive resist layer was developed with a 0.3% glycine aqueous solution. As a result, the laminate had a pattern having a circular opening. The SEM measurement was performed about the opening part of the obtained pattern. As a result, the opening diameter of the opening of the pattern of the heat-reactive resist layer was 200 nm, and insoluble matter derived from the interface layer was not confirmed at the bottom of the opening (recess).

Next, using this pattern as a mask, the etching layer was dry etched using SF ₆ gas under the conditions of power 300 W and gas pressure 5 Pa. When the obtained mold was observed by SEM, the mask was dry-etched during dry etching, and the heat-reactive resist material did not function as a mask.

Example 4
Three silicon substrates of 50 mmφ were prepared as base materials. On these three silicon substrates, SiO ₂ was sputtered as an etching layer under the conditions of an electric power of 100 W and an Ar gas pressure of 0.1 Pa to form 300 nm thick etching layers, respectively. Then, three silicon deposited etch layer on the substrate, respectively _{CuO-16mol% SiO 2, CuO} -35mol% SiO 2 and CuO-40mol% SiO _2, power 100W, a gas mixture of Ar and _{O 2} Sputtering was performed under the condition of a pressure of 0.1 Pa to form three types of heat-reactive resist layers having a thickness of 20 nm. In this manner, three types of laminates composed of a substrate, an etching layer, and a heat-reactive resist layer were produced.

Next, the heat-reactive resist layer of the laminate was exposed under the following conditions.
Semiconductor laser wavelength for exposure: 405 nm
Lens numerical aperture: 0.85
Exposure laser power: 1mW to 25mW
Feed pitch: 120 nm to 1000 nm

  Various shapes and patterns can be formed by modulating the intensity of the laser during exposure. In this embodiment, an isolated circle (opening diameter 180 nm) is used as the pattern in order to confirm the uniformity of the fine pattern. Formed. As a pattern shape to be formed, a continuous groove shape, an isolated elliptical shape, or the like can be selected depending on a desired application.

  Next, the heat-reactive resist layer of the above laminate was developed with a 0.3% glycine aqueous solution to form a pattern having a circular opening. SEM measurement was performed on the openings of the formed pattern. As a result, in each thermal reaction type resist layer, the opening diameter of the opening of the pattern was 180 nm, and insoluble matter derived from the interface layer was not confirmed at the bottom (concave) of the opening.

Next, using this pattern as a mask, the etching layer was removed by dry etching using SF ₆ gas under the conditions of power 300 W and gas pressure 5 Pa, and the mask was further removed to produce a mold. When the obtained mold was observed by SEM, it was found that a pattern having a uniform opening in the etching layer was obtained.

(Comparative Example 3)
Except for changing the composition of the thermal reaction type resist layer on the _{CuO-5mol% SiO 2, CuO} -10mol% SiO 2, CuO-45mol% SiO 2, CuO-50mol% SiO 2, CuO-55mol% SiO 2 , all carried out A laminate was produced under the same conditions as in Example 4.

Next, the heat-reactive resist layer of the laminate was exposed under the same conditions as in Example 4. Thereafter, the heat-reactive resist layer was developed with a 0.3% glycine aqueous solution. As a result, the laminated body using CuO-5 mol% SiO ₂ and CuO-10 ol% SiO ₂ as a resist obtained a pattern having a circular opening. The SEM measurement was performed about the opening part of the obtained pattern. As a result, the opening diameter of the opening of the pattern of the thermal reaction type resist layer was 180 nm, and insoluble matter derived from the interface layer was confirmed at the bottom of the opening (recess).

On the other hand, in the laminate using CuO-45 mol% SiO ₂ as a resist, a pattern having a circular opening was obtained. The SEM measurement was performed about the opening part of the obtained pattern. As a result, the opening diameter of the opening portion of the pattern of the thermal reaction type resist layer was 180 nm, and insoluble matter derived from the interface layer was not confirmed at the bottom portion (concave portion) of the opening portion. Next, using this pattern as a mask, the etching layer was dry etched using SF ₆ gas under the conditions of power 300 W and gas pressure 5 Pa. When the obtained mold was observed by SEM, the mask was dry-etched during dry etching, and the heat-reactive resist material did not function as a mask.

Further, _CuO-50mol% SiO 2, laminate using the CuO-55mol% SiO ₂ as a resist, since SiO2 addition amount is large, the pattern in the exposure power shortage was not able to form.

  From Examples 1 to 4 and Comparative Examples 1 to 3 described above, the following was confirmed. That is, it comprises an object to be processed and a heat-reactive resist layer provided directly on the surface of the object to be processed, and the heat-reactive resist layer is an etching material constituting the heat-reactive resist material and the object to be processed. And a dry etching laminate having an etching material ratio of more than 15 mol% and not more than 50 mol% is excellent in fine concavo-convex pattern forming ability and excellent in dry etching resistance, that is, mask performance. Thus, it was confirmed that the formation of the interface layer can be suppressed very well.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effects of the present invention are exhibited.

  The present invention can be applied to form a uniform fine concavo-convex pattern using dry etching on various objects to be processed. Is possible.

DESCRIPTION OF SYMBOLS 10 Laminated body for dry etching 11 Base material 12 Etching layer 13 Thermal reaction type resist layer 14 Mold

Claims (16)

  An object to be processed and a heat-reactive resist layer provided directly on the surface of the object to be processed. The heat-reactive resist layer is etched to form a heat-reactive resist material and the object to be processed. A dry etching laminate, wherein the etching material has a ratio of more than 15 mol% to 50 mol%.   2. The dry according to claim 1, wherein the heat-reactive resist material is made of a material having a boiling point of main fluoride of 250 ° C. or higher, and the etching material is made of a material having a boiling point of main fluoride of less than 250 ° C. Etching laminate.   3. The dry etching laminate according to claim 1, wherein the heat-reactive resist material and the etching material are incompatible with each other at a pattern forming temperature.   The dry etching laminate according to any one of claims 1 to 3, wherein the heat-reactive resist layer has a thickness of 5 nm to 1 µm.   The dry etching laminate according to any one of claims 1 to 4, wherein the object to be processed is an etching layer provided on a surface of a base material.   5. The dry etching laminate according to claim 1, wherein the object to be processed is a base material.   The laminate for dry etching according to claim 5 or 6, wherein the substrate has a flat plate shape, a cylindrical shape, or a lens shape.   A step of directly forming a heat-reactive resist layer containing a heat-reactive resist material and an etching material constituting the object to be processed and having a ratio of the etching material of more than 15 mol% and 50 mol% or less on the object to be processed Exposing the thermal reaction type resist layer; developing the thermal reaction type resist layer to form a mask; dry etching the object to be processed through the mask; and the thermal reaction And a step of obtaining a mold by removing the mold resist layer.   9. The method for producing a mold according to claim 8, wherein the thermal reaction type resist layer is provided by a sputtering method, a vapor deposition method or a CVD method.   The method for manufacturing a mold according to claim 8 or 9, wherein the object to be processed is an etching layer provided on a surface of a base material.   The method for manufacturing a mold according to claim 10, wherein the etching layer is provided by a sputtering method, a vapor deposition method, or a CVD method.   The mold manufacturing method according to claim 8, wherein the object to be processed is a base material.   The method for producing a mold according to any one of claims 10 to 12, wherein the base material has a flat plate shape, a cylindrical shape, or a lens shape.   The method for producing a mold according to any one of claims 8 to 13, wherein a semiconductor laser is used for exposure of the heat-reactive resist layer.   A mold manufactured by the method for manufacturing a mold according to any one of claims 8 to 14.   The mold according to claim 15, comprising a fine uneven pattern having a pitch of 1 nm to 1 μm.

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