JP2020042281A - Heat-reactive resist material, method for manufacturing mold using the same, and mold - Google Patents

Abstract

To provide a heat-reactive resist material capable of maintaining excellent pattern roughness even when a fine pattern is formed, a method for manufacturing a mold using the above material, and a mold.SOLUTION: The heat-reactive resist material of the present invention is a resist material comprising an amorphous oxide and characterized in that: a pattern is formed by using a phase change mode in which the material changes from an amorphous phase to a crystalline phase; and the material comprises, as the amorphous oxide, a composition of formula (1): CuOA, in which a part of or all of oxygen in copper (I) oxide is replaced by an element A. In formula (1), A represents at least one element selected from N, S and Se; x and y satisfy 0.35≤x+y≤0.65, 0≤x and 0<y and represent atomic ratios; and in formula (1), an atomic ratio of Cu:O:A is specified to 1:x:y.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a heat-reactive resist material, a method for manufacturing a mold using the same, and a mold.

  2. Description of the Related Art In recent years, as the demand for higher density and higher integration in the fields of semiconductors, optical / magnetic recording, and the like has increased, a fine pattern processing technique of several hundred nm to several tens nm or less has become essential.

  As a heat-reactive resist material used for fine pattern processing, an inorganic material having high dry etching resistance and capable of controlling the pattern size such as uniform unevenness and line shape has been disclosed by the present inventors (for example, , Patent Documents 1 and 2).

International Publication No. 2010/044400 pamphlet WO 2013/077266 pamphlet JP 2012-093678 A

  When an ultrafine pattern (for example, a pitch of 100 nm or less) is formed using an inorganic material as a resist, improvement in pattern roughness due to the influence of crystal grains of the inorganic material can be further studied.

  The present invention has been made in view of such a point, a heat-reactive resist material capable of maintaining excellent pattern roughness even when an ultrafine pattern is formed, a method of manufacturing a mold using the same, and a mold. The purpose is to provide.

The heat-reactive resist material of the present invention is a resist material made of an amorphous oxide, and forms a pattern using a phase change mode in which an amorphous oxide changes to a crystal. It is characterized by including a composition of the formula (1) in which a part or the whole is substituted by the element A.
CuO _x A _y (1)
However, A is at least one selected from N, S and Se,
0.35 ≦ x + y ≦ 0.65, 0 ≦ x, 0 <y. Further, x and y indicate the atomic ratio, and in the formula (1), the atomic ratio of Cu: O: A is set to 1: x: y.

  Further, the present invention is a manufacturing method for manufacturing a mold having an uneven shape on the surface of a substrate using the above-mentioned heat-reactive resist material, wherein the heat-reactive resist material is used on the base material. A step (1) of forming a reactive resist layer, a step (2) of exposing the heat-reactive resist layer to light, and developing with a developer; A step (3) of dry-etching the substrate with a gas; and a step (4) of removing the heat-reactive resist layer.

  Further, a mold of the present invention is characterized by being manufactured by the above-described method for manufacturing a mold.

  According to the present invention, it is possible to provide a heat-reactive resist material that can maintain excellent pattern roughness even when an ultrafine pattern is formed.

FIG. 1 is a cross-sectional view illustrating an example of a laminate using a heat-reactive resist according to an embodiment of the present invention. It is sectional drawing which showed the other example of the laminated body formed using the thermal reaction type resist concerning embodiment of this invention. It is sectional drawing which showed the other example of the laminated body using the thermal reaction type resist concerning embodiment of this invention. FIG. 3 is a schematic diagram showing a relationship between a spot diameter (irradiation area) of a laser beam and a temperature distribution within the spot diameter when a laser beam is irradiated on a heat-reactive resist material. It is sectional drawing which shows the manufacturing process of a fine pattern.

  The heat-reactive resist material of the present embodiment is a resist material made of an amorphous oxide, and is characterized in that a pattern is formed by using a phase change mode that changes from amorphous to crystalline. Here, the “phase change” is a physical change that changes from amorphous to crystalline, that is, changes in shape and state while maintaining the same chemical composition. On the other hand, oxidation and decomposition are chemical changes that result in different substances with a change in chemical composition. Therefore, when a pattern is formed using a heat-reactive resist material, it is necessary to select a material having a completely different concept between a material for forming a pattern by phase change and a material for forming a pattern by oxidation or decomposition. . Among them, the phase change is characterized in that it occurs at a relatively low temperature as compared with oxidation or decomposition, so that the particle growth of the resist material can be suppressed, which is suitable for forming a fine pattern. The amorphous or crystalline state of the heat-reactive resist material of the present embodiment can be analyzed by differential scanning calorimetry (DSC), X-ray diffraction measurement (XRD), or the like.

  The heat-reactive resist material of the present embodiment is preferably an amorphous oxide material containing at least one element in which the main fluoride has a boiling point of 200 ° C. or higher.

  When a fine pattern is formed using a heat-reactive resist material, there is a demand that the depth of the groove be increased to a desired depth along with the formation of the fine pattern. In this case, it is difficult to use the heat-reactive resist material alone, and a laminated structure in which an etching layer is formed below the heat-reactive resist material is required (the base material can also serve as the etching layer). . In this case, while the lower etching layer is being dry-etched, the heat-reactive resist material functioning as a mask is required to have high dry etching resistance. In other words, in the heat-reactive resist material according to the present embodiment, it is important that the etching rate of the heat-reactive resist material is low or not etched in the dry etching process using a chlorofluorocarbon-based gas.

  Here, when considering the mechanism of the dry etching by the chlorofluorocarbon-based gas, the fluorine activated in the vacuum chamber of the dry etching apparatus combines with the element used for the resist to form a fluoride. If the vapor pressure of the fluoride is relatively high (i.e., the boiling point of the fluoride is relatively low), the fluoride is vaporized and disappears from the resist material, resulting in etching. Become. On the other hand, when the vapor pressure of the fluoride is relatively low (that is, when the boiling point of the fluoride is relatively high), it is difficult to vaporize, so that the etching rate is reduced or the etching is not performed. The level of the vapor pressure is closely related to the boiling point of the fluoride.

The inventor of the present invention selects, from among the elements to be selected for the heat-reactive resist material, an element having a boiling point of 200 ° C. or higher as a heat-reactive resist material, whereby the resist material is made of fluorocarbon. It has been found that it exhibits high resistance to dry etching treatment using a system gas, and its effect has been confirmed. When the element forms a polyvalent fluoride, the boiling point of the fluoride means the boiling point of the main valence fluoride of the metal (= the boiling point of the main fluoride). For example, taking chromium as an example, chromium can have a valence of 0, 2, 3, or 6. For this reason, chromium fluoride can form CrF ₂ , CrF ₃ , and CrF _6. However, since the main valence of chromium is trivalent, the main fluoride of chromium refers to CrF ₃ , The boiling point of the main fluoride refers to the boiling point of CrF ₃ .

  The boiling point of the fluoride of the element constituting the heat-reactive resist material according to the present embodiment is 200 ° C. or higher, preferably 250 ° C. or higher, more preferably 700 ° C. or higher, still more preferably 800 ° C. or higher, and most preferably. Is 950 ° C. or higher. As the boiling point of the fluoride increases, the resistance to dry etching using a chlorofluorocarbon-based gas increases. The boiling points of the fluorides of the elements constituting the heat-reactive resist material according to the present embodiment can be selected with reference to Table 1 below.

  The amorphous oxide material used for the heat-reactive resist material of the present embodiment is a group IV element such as titanium oxide (IV), zirconium oxide (IV), hafnium oxide (IV), and an aluminum oxide group XIII. (III), gallium (III) oxide, indium (III) oxide and iron (III) oxide, cobalt (III) oxide, nickel (II) oxide, copper (I) oxide, zinc (II) oxide, tin oxide ( IV) and at least one selected from antimony (III) oxide, and titanium (IV) oxide, zirconium (IV) oxide, hafnium (IV) oxide, nickel (II) oxide, and copper (I) ) And zinc oxide (II), more preferably at least one selected from titanium (IV) oxide and zirconium oxide (IV), hafnium oxide (IV), nickel oxide (II), copper oxide (I), it is more preferably made of selected at least one or more of the zinc oxide (II). In particular, it is still more preferable that at least one selected from titanium oxide (IV), nickel oxide (II), copper oxide (I), and zinc oxide (II) is selected. Most preferably, it is selected. In limiting the above-mentioned preferable range, it can be selected from the viewpoint that a change from an amorphous state to a crystalline state occurs more quickly and that the developing characteristics are good. Note that titanium (IV), nickel (II) oxide, copper (I) oxide, and zinc (II) oxide change very rapidly from amorphous to crystalline, and among them, copper (I) oxide is the fastest. A faster change from amorphous to crystalline is more suitable for forming an ultrafine pattern while maintaining pattern roughness. Here, the speed of changing from amorphous to crystalline depends on the size of the energy barrier when changing from amorphous to crystalline. As a factor that greatly affects the size of the energy barrier, there is a difference between a structure formed in an amorphous state and a structure formed in a crystalline state. In other words, the more similar the structures in the amorphous state and the crystalline state are, the smaller the energy barrier is, and the speed of changing from amorphous to crystalline can be increased. In addition, since the energy barrier is small, the temperature required when changing from amorphous to crystalline can be kept low. The present inventor has focused on the fact that even in the amorphous state, the atomic arrangement is not completely random, but has a periodic structure within a certain probability range. It was found that a material having the same value as described above had a high rate of change from an amorphous state to a crystalline state and had a low temperature, and it was proved by an experiment that an ultrafine pattern which actually maintained the pattern roughness could be formed. Therefore, in the heat-reactive resist material using the phase change mode according to the present embodiment, it is preferable that the atomic arrangement in the amorphous state is close to that in the crystalline state.

This embodiment will be described in detail below. Thermal reaction type resist material according to this embodiment, the density is greater than 4.00 g / cm ^3, preferably contains 6.07 g / cm ³ less than copper oxide (I).

The general physical properties of copper (I) oxide are such that the melting point is 1232 to 1235 ° C., the boiling point (decomposition) is 1800 ° C., and the density is 6.04 g / cm ³ . On the other hand, when copper (I) oxide is used as the heat-reactive resist material, it is difficult to use it in bulk, so that it can be used, for example, as a thin film. The thin film is manufactured by using a method such as coating or physical vapor deposition, and when these methods are used, the density changes. Also in the case of copper (I) oxide, the density decreases when copper or oxygen escapes from the stoichiometric composition, and conversely, the density increases when it enters excessively, and exceeds the bulk density depending on conditions. In addition, the density also changes when a carrier gas used at the time of vapor deposition is taken into the thin film. In addition, there are simply sparse voids in the thin film, reducing the density of the thin film. The present inventor has found that the density of the thin film has a significant effect when forming an ultrafine pattern using a heat-reactive resist material.

  Here, the formation of the fine pattern using the heat-reactive resist material involves developing a fine pattern by applying a developing solution to a difference between a portion where the heat-reactive resist material is deteriorated by heat and a portion where the heat-reactive resist material is not deteriorated. To achieve. At this time, the heat also transfers heat to an adjacent portion that is not desired to be deteriorated, so that the resolution of the fine pattern, that is, the roughness is reduced. In particular, it has been found that when forming an ultrafine pattern, a portion that is desired to be deteriorated by heat and a portion that is not desired to be deteriorated come close to each other, so that the influence of heat transfer becomes remarkable, which greatly affects the resolution of the fine pattern.

The present inventor has conducted intensive studies and repeated experiments to solve such a problem. As a result, in the thermally reactive resist material containing copper oxide (I), the density of copper oxide (I) was increased from 4.00 g / cm ³ . It has been found that an ultra-fine pattern with a pitch of 100 nm or less can be formed by making it large and smaller than 6.07 g / cm ³ . The density of copper (I) oxide according to the present embodiment, 4.20 g / cm ³ or more, more preferably 5.95 g / cm ³ or less, 4.40 g / cm ³ or more, 5.95 g / cm ³ or less more preferably, 4.60 g / cm ³ or more, more preferably more that 5.95 g / cm ³ or less, 4.85 g / cm ³ or more, more preferably 5.95 g / cm ³ or less, 5.05 g / cm ³ or more, 5.95 g / cm ³ is more preferable less, 5.20 g / cm ³ or more, even more preferably from 5.90 g / cm ³ or less, 5.20 g / cm ³ or more, and most preferably 5.75 g / cm ³ or less . When a heat-reactive resist material to which an additive described later is added is used, the density of copper (I) oxide including the additive is preferably within the above range.

  If the density is too high, the influence of heat transfer is large and the pattern roughness is deteriorated, or the formation of an ultrafine pattern is hindered. On the other hand, if the density is too low, an ultrafine pattern can be formed, but there are many voids in the pattern portion, resulting in a state of voids, which deteriorates the pattern roughness, or a space for growing particles is secured due to the large number of voids. And the pattern roughness deteriorates. The density of copper (I) oxide according to the present embodiment can be selected according to desired conditions. On the other hand, in a widely used photoresist material, since the reaction mechanism is light rather than heat, the influence of the resist density on the pattern roughness does not occur. Therefore, no study on such resist density has been made so far.

  In the heat-reactive resist material, the density of copper (I) is determined by Rutherford Backscattering Spectrometry (RBS), X-ray Reflectometry (XRR), or Ellipsometry. (Measurement).

  By using a material in this density range as a heat-reactive resist material, good pattern roughness can be exhibited even in an ultrafine pattern with a pitch of 100 nm or less. “Pattern roughness” refers to the roughness of the pattern shape, and refers to the degree of deviation from a reference line drawn on the pattern side wall (in the case of line and space, the reference line is a straight line), and the pattern side wall is The closer it means, the smaller the unevenness and the smoother the surface.

  Patent Document 3 discloses that reoxidation of copper oxide can be suppressed by adding a reoxidation inhibitor to copper (I) oxide. By mixing the antioxidant with copper (I) oxide, the antioxidant effect becomes very high. However, there is no mention of controlling the density of copper (I) oxide in an appropriate range to form an ultrafine pattern while maintaining good pattern roughness. In addition, since copper (I) oxide corresponds to a material having high dry etching resistance using a chlorofluorocarbon-based gas disclosed in Patent Document 1, the thermally reactive resist material according to the present embodiment is a chlorofluorocarbon-based gas. With high dry etching resistance.

From the above, the thermal reaction type including the copper (I) oxide according to the present embodiment and having the density of the copper (I) oxide larger than 4.00 g / cm ^{3 and} smaller than 6.07 g / cm ³ is satisfied. The resist material is a material having a very high value as a mask for an ultrafine pattern.

  The average particle size of the copper (I) oxide of the present embodiment is preferably 10 nm or less. This is because the influence of the particle size on pattern roughness can be minimized in forming an ultrafine pattern.

  Here, a case where the average particle size of 20 nm is used will be described. When a pattern having a relatively large pattern pitch of 800 nm and a duty of 50 is formed, the width of the projection is 400 nm. The projections are formed of copper (I) oxide particles. When the particle size is 20 nm, a pattern roughness of about 5% is provided at the maximum, and the influence is small. On the other hand, when a pattern with a pitch of 100 nm and a duty of 50 is formed as an ultrafine pattern, the width of the convex portion becomes 50 nm, giving a pattern roughness of about 40% at the maximum, which is extremely large.

  From the above, the particle size of the copper oxide (I) for the ultrafine pattern of the present embodiment is 10 nm or less on average, preferably 8 nm or less on average, more preferably 5 nm or less on average, and most preferably. Is 4 nm or less on average. The smaller the particle size of the copper (I) oxide, the smaller the effect on the pattern roughness, and an excellent pattern roughness can be achieved. Note that the copper (I) oxide particles are amorphous and can be less affected by the particle size than in the crystalline state.

  The particle size of copper (I) oxide according to the present embodiment can be measured using a morphological analyzer such as a TEM. The average particle size of this embodiment is determined by using TEM analysis, selecting 20 copper oxide (I) particles from the obtained image, averaging the maximum length and the minimum length of each particle, Further, it is a value obtained by averaging 20 pieces.

  Copper (I) oxide used in the heat-reactive resist material according to the present embodiment is, as an additive, at least one or more from the group (A) consisting of sodium, lithium, potassium, and their halides and oxides. In addition, it is preferable that at least one or more from the group (B) consisting of Group V, Group VI, Group XIV, and oxides and nitrides thereof are added. By adding the additive, it is possible to finely control the particle size of copper (I) oxide and improve the developing characteristics when forming an ultrafine pattern. From the group (A), the additive is more preferably sodium and its oxide. In addition, from the group (B), it is preferable to add at least one of niobium and tantalum from the group V, molybdenum from the group VI, silicon and germanium from the group XIV, and oxides and nitrides thereof. Further, it is more preferable that at least one or more of niobium from group V and silicon, germanium, and oxides thereof from group XIV are added. More preferably, at least one or more of oxides of niobium from group V and silicon from group XIV are added. Most preferably, a silicon oxide is added from Group XIV. As an additive, an oxide is preferable because it is easier to control when forming a heat-reactive resist material than a metal element or a nitride. By selecting the material from the group (A), the developing characteristics at the time of forming an ultrafine pattern are improved, and by selecting the material from the group (B), the particle size can be reduced.

  The reason why sodium and its oxide are preferable in the additive of the group (A) to the copper (I) oxide according to the present embodiment will be described in detail below. Copper (I) oxide generally uses a material containing sodium during the course of synthesis, so that sodium and its oxide tend to remain. Therefore, by selecting sodium and its oxide as an additive, sodium and its oxide contained in the raw material can exert the effects of the present embodiment without adding an additive, which is preferable. From the above, the addition according to the present embodiment refers to the range of addition of the impurity originally contained in the raw material, and can be further added in accordance with the ratio contained in the raw material.

  On the other hand, it is possible to synthesize copper (I) oxide containing no sodium by using a special synthesis method, and there is a commercially available product. Using this copper (I) oxide, an additive can be added. However, copper oxide (I) using a special synthesis method is expensive, so that copper oxide (I) containing sodium and its oxide and copper oxide (I) containing no sodium and its oxide as necessary. ). Further, as a method of synthesizing copper (I) containing no sodium and its oxide, when forming a resist layer made of a heat-reactive resist material, copper (I) is not used as a starting material and metal is used. There is also a method of using copper and oxidizing the copper during the film formation process to obtain copper (I) oxide. In this case, there is no problem in cost. On the other hand, from the viewpoint of controlling the amount of oxygen in film formation, fine adjustment is required as compared with the method using copper (I) oxide as a starting material. If necessary, a method using copper oxide (I) as a starting material and a method using metallic copper as a starting material may be used properly. It is preferable to use copper (I) oxide produced by a general synthesis method as the heat-reactive resist material according to the present embodiment.

The amount of the additive according to the present embodiment is not particularly limited when the density of copper (I) is in a range of greater than 4.00 g / cm ^{3 and} less than 6.07 g / cm ^3. If the amount is too small, the effect is small, and if the amount is too large, the effect cannot be exhibited. Therefore, the proportion of the additive in group (A) is 0.0002 mol% or more and 5.8 mol% or less, and the proportion of the additive in group (B) is 5.8 mol% or more and 26.1 mol with respect to copper (I) oxide. % Is preferable. More preferably, the ratio of the additive in the group (A) is 0.0002 mol% or more and 4.0 mol% or less, and the ratio of the additive in the group (B) is 9.5 mol% or more and 21.5 mol% or less. Most preferably, the proportion of the additive of A) is from 0.0002 mol% to 2.0 mol%, and the proportion of the additive of group (B) is from 9.5 mol% to 18.2 mol%.

  Further, with respect to Cu, the ratio of the additive in the group (A) is 0.0001 mol% or more and 3.0 mol% or less, and the ratio of the additive in the group (B) is 3.0 mol% or more and 15.0 mol% or less. Preferably, there is. More preferably, the ratio of the additive in the group (A) is 0.0001 mol% or more and 2.0 mol% or less, and the ratio of the additive in the group (B) is 5.0 mol% or more and 12.0 mol% or less. Most preferably, the proportion of the additive in A) is from 0.0001 mol% to 1.0 mol%, and the proportion of the additive in group (B) is from 5.0 mol% to 10.0 mol%.

In the case where a plurality of additives are selected in the additive to copper (I) oxide according to the present embodiment, the total ratio of the plurality of additives is preferably within the range of the additives. Note that the additive to the copper (I) oxide according to the present embodiment can be selected according to desired conditions, and niobium or silicon oxide is preferable as the effect of suppressing the particle size. When SiO ₂ or quartz is used as the material, silicon oxide is preferable from the viewpoint of affinity, and chromium (Cr) and its oxide and nitride are preferable as the effect of increasing the dry etching resistance of the resist.

  In the formation of a fine pattern using copper (I) oxide according to the present embodiment, as described above, the phase change mode in which thermal deterioration due to exposure changes from non-crystalline (amorphous) to crystalline. Thereby, since the phase change of copper (I) oxide occurs at a relatively low temperature, the growth of coarse particles can be suppressed, which is suitable for forming a fine pattern.

  As described above, the heat-reactive resist material containing copper (I) oxide according to the present embodiment has high resistance to dry etching using a chlorofluorocarbon-based gas. When it is desired to form a pattern in which the depth of the groove is increased to a desired depth together with the fine pattern shape, it is difficult to use only the heat-reactive resist material alone, and an etching layer is formed below the heat-reactive resist material. A laminated structure is required. In this case, while the lower etching layer is being dry-etched, the heat-reactive resist material functioning as a mask is required to have high dry etching resistance.

Further, the heat-reactive resist material according to the present embodiment preferably contains a composition of the formula (1) in which part or all of oxygen of copper (I) oxide is replaced by element A.
CuO _x A _y (1)
Here, A is at least one selected from N, S, and Se, and 0.35 ≦ x + y ≦ 0.65, 0 ≦ x, and 0 <y. Further, x and y indicate the atomic ratio, and in the formula (1), the atomic ratio of Cu: O: A is set to 1: x: y.

  Copper oxides include copper (I) oxide and copper (II) oxide as oxides having a stoichiometric composition, and other oxides having an oxidation number other than the stoichiometric composition as incomplete copper oxides.

  Above all, an oxide having a stoichiometric composition is in a state where the material itself can be stably present, so that it does not easily change over time and is excellent in production stability. In the stoichiometric copper (I) oxide having excellent production stability, part or all of oxygen can be replaced by one or more elements A selected from N, S, and Se. It has been found that the replaced copper (I) hardly changes with time even in the vicinity of the stoichiometric composition, and has been found to be excellent in production stability. That is, when the content is in the range of the above-described formula (1), extremely excellent production stability can be obtained.

  Here, by selecting at least one element selected from N, S, and Se as the element A, the amount of heat absorbed by the copper (I) oxide can be controlled during the formation of the fine pattern, so that the efficiency is improved. The resist can often be altered by heat.

  Furthermore, it has been found that by adjusting the composition within the above-described composition range, good pattern roughness can be exhibited even in a fine pattern having a pitch of 100 nm or less. "Pattern roughness" refers to the degree of deviation from a reference line drawn on the pattern side wall (in the case of line and space, the reference line is a straight line). Is smooth.

  By the way, Patent Document 3 discloses that reoxidation of copper oxide can be suppressed by adding an additive to copper (I) oxide. By mixing the additive with copper (I) oxide, the effect of preventing oxidation is extremely enhanced.

  On the other hand, the present embodiment is characterized in that part or all of oxygen of copper (I) oxide is replaced with one or more elements A selected from N, S and Se. . As a result, a fine pattern can be formed with higher precision while maintaining good pattern roughness as compared with the related art. In addition, copper (I) oxide corresponds to a material having high dry etching resistance using a chlorofluorocarbon-based gas, and the heat-reactive resist material of the present embodiment has high dry etching resistance using a chlorofluorocarbon-based gas.

As described above, CuO _x A _y (where A is one or more selected from N, S, and Se, in which a part or all of oxygen of copper oxide (I) is substituted by element A, (35 ≦ x + y ≦ 0.65, 0 ≦ x, 0 <y)) is a highly useful material as a mask for a fine pattern.

  Here, when x + y is smaller than 0.35 and x + y is larger than 0.65, it becomes difficult to form a copper (I) oxide bonding structure, so that the resist characteristics are deteriorated. Specifically, when x + y is smaller than 0.35, the proportion of the copper-copper bonding structure increases due to an increase in the copper ratio. On the other hand, when x + y is larger than 0.65, the proportion of the bond structure of copper (II) increases due to an increase in the proportion of oxygen and / or element A. When the bonding structure changes, the bonding state at the atomic level changes, which greatly affects resist characteristics.

In the present embodiment, in order to form a finer pattern while maintaining good pattern roughness, the composition is CuO _x A _y (A is at least one selected from N, S and Se; More preferably, 0.35 ≦ x + y ≦ 0.65, 0 ≦ x, 0 <y), and the composition comprises CuO _x A _y (A is N, and 0.35 ≦ x + y ≦ 0.65, More preferably, 0 ≦ x, 0 <y), and the composition is CuO _x A _y (A is N, and 0.45 ≦ x + y ≦ 0.55, 0 ≦ x, 0 <y). Is most preferred.

  The method for substituting a part or all of the oxygen of the copper (I) oxide with the element A is not particularly limited. For example, when a heat-reactive resist material is prepared by a sputtering method, the element A may be added or added. A method in which a material fired in an atmosphere of the element A is used as a target, or a method in which copper (I) oxide not substituted with the element A is used as a target and a gas containing the element A is used as a process gas during sputtering is used. can do. When a heat-reactive resist material is prepared by using a coating method, a method using a coating solution containing element A, or a coating solution containing no element A, and an atmosphere containing element A at the time of subsequent thin film baking And the like.

As described above, by using a heat-reactive resist material containing a composition of CuO _x A _y (A is N and 0.45 ≦ x + y ≦ 0.55, 0 ≦ x, 0 <y), light Can be optimized, and the exposure characteristics of the heat-reactive resist material can be effectively improved. Note that the constituent elements and the composition ratio of the composition in this embodiment can be selected depending on desired conditions.

The state of the composition composed of CuO _x A _y is not particularly specified as long as it satisfies the above formula (1). For example, when a thin film of the composition is taken as an example, the composition has a uniform composition in the film thickness direction. Or a state in which the amount of the element A gradually increases and decreases in the film thickness direction. The copper (I) oxide layer containing no element A and the composition layer made of CuO _x A _y May be alternately stacked. In such a laminated structure, it is sufficient that the average composition of the respective layers constitutes the composition represented by the above formula (1).

Whether or not the composition is CuO _x A _y can be confirmed by XRD (X-ray Diffraction) analysis, XPS (X-ray Photoelectron Spectroscopy) analysis, or the like.

Thermal reaction type resist material according to this embodiment, the density is greater than 4.00 g / cm ^3, a part or all of oxygen of 6.07 g / cm ³ less than copper (I) oxide is replaced with the element A It is preferable to contain a composition of CuO _x A _y satisfying the formula (1).

The general physical properties of copper (I) oxide are such that the melting point is 1232 to 1235 ° C., the boiling point (decomposition) is 1800 ° C., and the density is 6.04 g / cm ³ . On the other hand, when copper (I) oxide is used as the heat-reactive resist material, it is difficult to use it in bulk, so that it can be used, for example, as a thin film. The thin film is manufactured by using a method such as coating or physical vapor deposition, and when these methods are used, the density changes. Also in the case of copper (I) oxide, the density decreases when copper or oxygen escapes from the stoichiometric composition, and conversely, the density increases when it enters excessively, and exceeds the bulk density depending on conditions. In addition, the density also changes when a carrier gas used at the time of vapor deposition is taken into the thin film. In addition, there are simply sparse voids in the thin film, reducing the density of the thin film. The present inventor has found that the density of the thin film has a significant effect when forming an ultrafine pattern using a heat-reactive resist material.

  Here, the formation of the fine pattern using the heat-reactive resist material involves developing a fine pattern by applying a developing solution to a difference between a portion where the heat-reactive resist material is deteriorated by heat and a portion where the heat-reactive resist material is not deteriorated. To achieve. At this time, the heat also transfers heat to an adjacent portion that is not desired to be deteriorated, so that the resolution of the fine pattern, that is, the roughness is reduced. In particular, it has been found that when forming an ultrafine pattern, a portion that is desired to be deteriorated by heat and a portion that is not desired to be deteriorated come close to each other, so that the influence of heat transfer becomes remarkable, which greatly affects the resolution of the fine pattern.

The inventor of the present invention has conducted intensive studies and repeated experiments to solve such a problem. As a result, the density of CuO _x A _y in the heat-reactive resist material containing the composition of CuO _x A _y satisfying the above-mentioned formula (1) was determined. the greater than 4.00 g / cm ^3, to be smaller than 6.07 g / cm ^3, it was found that it is possible to form the following ultrafine pattern pitch 100 nm. Density of _CuO x _{A y} in accordance with the present embodiment, 4.20 g / cm ³ or more, more preferably 5.95 g / cm ³ or less, 4.40 g / cm ³ or more, 5.95 g / cm ³ or less is more preferably, 4.60 g / cm ³ or more, more preferably more that 5.95 g / cm ³ or less, 4.85 g / cm ³ or more, more preferably 5.95 g / cm ³ or less, 5.05 g / cm ³ or more, 5 .95g / cm ³ is more preferable less, 5.20 g / cm ³ or more, 5.90 g / cm ³ is even more preferable less, 5.20 g / cm ³ or more, 5.75 g / cm ³ or less is most preferred. When using the thermal reaction type resist material obtained by adding an additive, it is preferable density of CuO _x A _y, including additives within the above range.

If the density is too high, the influence of heat transfer is large and the pattern roughness is deteriorated, or the formation of an ultrafine pattern is hindered. On the other hand, if the density is too low, an ultrafine pattern can be formed, but there are many voids in the pattern portion, resulting in a state of voids, which deteriorates the pattern roughness, or a space for growing particles is secured due to the large number of voids. And the pattern roughness deteriorates. The density of CuO _x A _y according to the present embodiment can be selected according to desired conditions. On the other hand, in a widely used photoresist material, since the reaction mechanism is light rather than heat, the influence of the resist density on the pattern roughness does not occur. Therefore, no study on such resist density has been made so far.

In the heat-reactive resist material, the density of CuO _x A _y can be determined by Rutherford Backscattering Spectrometry (RBS), X-ray reflectometry (XRR: X-Ray Reflection), or ellipsometry (Ellipsometry). ).

  By using a material in this density range as a heat-reactive resist material, good pattern roughness can be exhibited even in an ultrafine pattern with a pitch of 100 nm or less.

The heat-reactive resist material according to the present embodiment includes Na, Mg, Si, Sr, V, Cr, Mo, W, Ag, Zn, Ga, together with the composition of CuO _x A _y satisfying the above-described formula (1). It is preferable that one or more of Ge, Nb, Ta and their oxides, nitrides, and oxynitrides be included as an additive. By adding the additive, development characteristics at the time of forming a fine pattern can be improved, and a fine pattern having excellent pattern roughness can be obtained.

  More preferably, the additive contains at least one of Na, Si, V, Cr, Mo, W, Zn, Ge and its oxides, nitrides, and oxynitrides. Further, it is more preferable that at least one of Na, Si, Mo, W and its oxide, nitride, and oxynitride is contained. Most preferably, at least one of Si and its oxide, nitride, and oxynitride is contained. By including at least one of Si and its oxides, nitrides, and oxynitrides, it is possible to more effectively improve development characteristics at the time of forming a fine pattern, and to obtain a fine pattern with more excellent pattern roughness. It becomes possible.

The amount of the additive to be added to the composition of CuO _x A _y according to the present embodiment will be described. The amount of the additive is not particularly specified, but if the amount is too small, the effect of improving the developing characteristics is small, and if the amount is too large, the resist characteristics deteriorate. Therefore, the amount of the additive is 2.0 mol% or more and 30.0 mol% or less with respect to the composition of CuO _x A _y , that is, with respect to Cu, when the entire heat-reactive resist material is 100 mol%. It is. 3.0 mol% or more and 20.0 mol% or less are preferable. Further, the content is more preferably 4.0 mol% or more and 15.0 mol% or less. Further, the content is more preferably 5.0 mol% or more and 12.0 mol% or less. Further, the content is most preferably 6.0 mol% or more and 10.0 mol% or less.

Further, the proportion of the additive is preferably 3.9 mol% or more and 46.2 mol% or less with respect to the chemical formula Cu ₂ O _2x A _{2y in} which copper (I) oxide is considered as a structural unit. The ratio of the additive is more preferably 5.8 mol% or more and 33.3 mol% or less. Further, the content is more preferably from 7.7 mol% to 26.1 mol%. Further, the content is more preferably 9.5 mol% or more and 21.4 mol% or less. Most preferably, it is 11.3 mol% or more and 18.2 mol% or less.

Alternatively, the composition of CuO _x A _y that satisfies the above-described formula (1) used in the heat-reactive resist material according to the present embodiment includes Na, Li, K, and their halides and oxides as additives. It is preferable to add at least one or more from the group (A) consisting of a substance, and at least one or more from the group (B) consisting of a group V, a group of VI, a group of XIV, and oxides and nitrides thereof. . By adding the additives from the groups (A) and (B), the particle size of the copper (I) oxide can be finely controlled and the developing characteristics at the time of forming an ultrafine pattern can be improved.

  From the group (A), the additive is more preferably sodium (Na) and its oxide. From group (B), group V to niobium (Nb), tantalum (Ta), group VI to molybdenum (Mo), group XIV to silicon (Si), germanium (Ge), and at least from oxides and nitrides thereof. More preferably, one or more are added. More preferably, at least one or more of niobium from group V and silicon, germanium, and oxides thereof from group XIV are added. Further, it is even more preferable that at least one of niobium from group V, silicon from group XIV, and oxides thereof is added. Most preferably, a silicon oxide is added from Group XIV. An oxide is preferred as an additive because it is easy to control when forming a heat-reactive resist material. By selecting the material from the group (A), the developing characteristics at the time of forming an ultrafine pattern are improved, and by selecting the material from the group (B), the particle size can be reduced.

The reason why sodium and its oxide are preferable in the additive of the group (A) to the composition of CuO _x A _y satisfying the above formula (1) according to the present embodiment will be described in detail below. Copper (I) oxide in which oxygen is not replaced with the element A generally uses a material containing sodium during the course of synthesis, and thus sodium and its oxide tend to remain. Therefore, by selecting sodium and its oxide as an additive, sodium and its oxide contained in the raw material can exhibit the effects of the present embodiment without adding an additive, which is preferable. From the above, the addition according to the present embodiment refers to the range of addition of the impurity originally contained in the raw material, and can be further added in accordance with the ratio contained in the raw material.

  On the other hand, it is possible to synthesize copper (I) oxide containing no sodium by using a special synthesis method, and there is a commercially available product. Using this copper (I) oxide, an additive can be added. However, copper oxide (I) using a special synthesis method is expensive, so that copper oxide (I) containing sodium and its oxide and copper oxide containing no sodium and its oxide may be used as necessary. (I) may be used properly. Further, as a method of synthesizing copper (I) containing no sodium and its oxide, when forming a resist layer made of a heat-reactive resist material, copper (I) is not used as a starting material and metal is used. There is also a method of using copper and oxidizing the copper during the film formation process to obtain copper (I) oxide. In this case, there is no problem in cost. On the other hand, from the viewpoint of controlling the amount of oxygen in film formation, fine adjustment is required as compared with the method using copper (I) oxide as a starting material. If necessary, a method using copper (I) oxide as a starting material and a method using metallic copper as a starting material may be used properly. It is preferable to use copper (I) oxide produced by a general synthesis method for the heat-reactive resist material according to the present embodiment.

The amount of the additive according to the present embodiment is set so that the density of the composition of CuO _x A _y satisfying the above-described formula (1) is larger than 4.00 g / cm ^{3 and} smaller than 6.07 g / cm ^3. In some cases, there is no particular limitation, but if the amount is too small, the effect is small, and if the amount is too large, the effect cannot be exerted. Therefore, the ratio of the additive of the group (A) to the composition of CuO _x A _y that satisfies the above formula (1), that is, to Cu, is 0.0001 mol% or more and 3.0 mol% or less. The proportion of the additive (B) is preferably from 3.0 mol% to 15.0 mol%. More preferably, the ratio of the additive in the group (A) is 0.0001 mol% or more and 2.0 mol% or less, and the ratio of the additive in the group (B) is 5.0 mol% or more and 12.0 mol% or less. Most preferably, the proportion of the additive in A) is from 0.0001 mol% to 1.0 mol%, and the proportion of the additive in group (B) is from 5.0 mol% to 10.0 mol%.

Further, for the chemical formula Cu ₂ O _2x A _{2y in} which copper (I) oxide is considered as a structural unit, the ratio of the additive in the group (A) is 0.0002 mol% or more and 5.8 mol% or less, and the group (B) Is preferably 5.8 mol% or more and 26.1 mol% or less. More preferably, the ratio of the additive in the group (A) is 0.0002 mol% or more and 4.0 mol% or less, and the ratio of the additive in the group (B) is 9.5 mol% or more and 21.5 mol% or less. Most preferably, the proportion of the additive of A) is from 0.0002 mol% to 2.0 mol%, and the proportion of the additive of group (B) is from 9.5 mol% to 18.2 mol%.

In the additive in the composition of CuO _x A _y satisfying the equation (1) according to this embodiment, if you select multiple, it is preferred that the total proportion of multiple additives is in the range of the additive. The additive to the composition of CuO _x A _y that satisfies the formula (1) according to the present embodiment can be selected according to desired conditions, and the effect of suppressing the particle size is niobium or silicon. When SiO ₂ or quartz is used for the base material, silicon oxide is preferable from the viewpoint of affinity. The effect of increasing the dry etching resistance of the resist is chromium (Cr) and its oxides and Preferably, at least one or more are added from nitride.

In the formation of a fine pattern using the composition of CuO _x A _y that satisfies the formula (1) according to the present embodiment, a phase change mode in which thermal deterioration due to exposure changes from non-crystalline (amorphous) to crystalline. . Thereby, since the phase change of the composition of CuO _x A _y satisfying the formula (1) occurs at a relatively low temperature, the growth of coarse particles can be suppressed, which is suitable for forming a fine pattern.

As described above, the heat-reactive resist material containing the composition made of CuO _x A _y of the present embodiment has high resistance to dry etching using a chlorofluorocarbon-based gas. When it is desired to form a pattern in which the depth of the groove is increased to a desired depth together with the fine pattern shape, it is difficult to use only the heat-reactive resist material alone, and an etching layer is formed below the heat-reactive resist material. A laminated structure is required. In this case, while the lower etching layer is being dry-etched, the heat-reactive resist material functioning as a mask is required to have high dry etching resistance.

  As described above, since the heat-reactive resist material according to the present embodiment has high resistance to dry etching using a chlorofluorocarbon-based gas, the aspect ratio (the value obtained by dividing the groove depth by the pattern width) is used. Can be freely selected, which increases the degree of freedom in design. Therefore, it is important that the heat-reactive resist material according to the present embodiment has high dry etching resistance. Further, the dry etching layer is preferably made of a material having a higher dry etching rate than the resist layer.

  As an etching material forming the etching layer, it is preferable to select a material having a low boiling point of a main fluoride of the selected element. Specifically, at least one of oxides, nitrides, sulfides, carbides, and silicides of one or more materials selected from elements in which the boiling point of the fluoride is less than 250 ° C. preferable. This can be referred to the index of selection of the etching material of the dry etching layer disclosed in Patent Document 1.

Specifically, the etching material according to this embodiment includes Ta, Mo, W, C, Si, Ge, Te, and P, and a composite of two or more of them, and an oxide, a nitride, and a composite thereof. A material that can be selected from the group consisting of carbonates, and preferably consists of Ta, Si, Ge, and P and their oxides, nitrides, sulfides, and carbonates, and Mo, W silicides. It is a material selected from the group, more preferably a material selected from the group consisting of Ta, Si, Ge, and P, and oxides and nitrides thereof. Particularly preferred are SiO ₂ , Si, and Si ₃ N ₄ , and most preferred is SiO ₂ , particularly from the viewpoint of ease of film formation, stability over time, strength, cost, adhesion, and the like.

  So far, the importance of the etching layer has been described in order to make the aspect ratio a desired value. However, it is also possible to form a uniform pattern by integrating the base material with the etching layer.

  Subsequently, a method for manufacturing a mold using the heat-reactive resist material according to the present embodiment will be described.

  First, as a first step, a heat-reactive resist layer is formed on a substrate. Subsequently, as a second step, the heat-reactive resist layer is exposed and then developed with a developer. Subsequently, as a third step, a fine pattern is formed by dry-etching the base material using a CFC-based gas with the developed heat-reactive resist as a mask. Subsequently, as a fourth step, the heat-reactive resist is removed to manufacture a mold.

  In the case where a heat-reactive resist layer is formed in the first step, film formation using a sputtering method, an evaporation method, or a CVD method is preferable. Since the heat-reactive resist material is capable of processing a fine pattern on the order of several tens of nanometers, the film thickness distribution and surface irregularities of the heat-reactive resist material at the time of film formation greatly affect the fine pattern size. It is possible. Therefore, in order to reduce these effects as much as possible, a film forming method such as a sputtering method, a vapor deposition method, a CVD method, or the like is used instead of a film forming method such as a coating method or a spray method in which it is somewhat difficult to control the uniformity of the film thickness. It is preferable to form a heat-reactive resist material by the above method. In particular, the sputtering method is most preferable for controlling the density of the thin film. In the sputtering method, the density of the thin film can be controlled by controlling the sputtering conditions, that is, the sputtering pressure, the input power during film formation, the distance and angle between the substrate and the target, the substrate temperature, the sintering density of the target, and the like. .

  FIG. 1 is a cross-sectional view showing an example of a laminate using the heat-reactive resist according to the embodiment of the present invention. In the present embodiment, the resist layer composed of the heat-reactive resist material may be a single layer, and as shown in FIG. (A structure in which a layer 2 is formed and a first resist layer 3a and a second resist layer 3b are sequentially formed on the etching layer 2). Note that what kind of resist is selected can be appropriately changed depending on the process, required processing accuracy, and the like.

  The heat-reactive resist layer may be provided with a heat dissipation design as needed. The heat radiation design is designed when it is necessary to release heat from the heat-reactive resist material as soon as possible. For example, the heat dissipation design is performed when the heat reaction progresses in a wider area than the spot shape of the heat reaction due to the exposure due to the accumulation of heat.

  FIG. 2 is a cross-sectional view showing another example of the laminate using the heat-reactive resist according to the embodiment of the present invention. FIG. 3 is a cross-sectional view showing another example of the laminate using the heat-reactive resist according to the embodiment of the present invention. The heat dissipation design is such that a material layer 5 having a higher thermal conductivity than air is formed above the resist layer 3 made of a heat-reactive resist material (see FIG. 2; ), Or a material layer 5 having a higher thermal conductivity than the base material 1 below the resist layer 3 made of a heat-reactive resist material (see FIG. 3, FIG. 2 indicate the same layer as in FIGS. 1 and 2).

  The thickness of the resist layer made of the heat-reactive resist material according to the present embodiment is preferably 10 nm or more and 100 nm or less. Heating of the heat-reactive resist material is achieved by absorption of light such as exposure by the heat-reactive resist material to change into heat. Therefore, in order to achieve heating, the heat-reactive resist material needs to absorb light, and the amount of light absorbed greatly depends on the film thickness. When the thickness of the resist layer made of a heat-reactive resist material is 10 nm or more, the amount of light absorption increases, and thus heating becomes easy and efficient. Therefore, the thickness of the resist layer made of the heat-reactive resist material according to the present embodiment is preferably 10 nm or more. Even when the film thickness is small, the amount of light absorbed can be compensated for by disposing a light absorbing layer or the like above and / or below the resist layer made of the heat-reactive resist material.

  On the other hand, by setting the thickness of the resist layer made of the heat-reactive resist material to 100 nm or less, uniformity in the thickness direction by exposure can be appropriately secured. That is, not only the depth direction but also the processing accuracy of the fine pattern in the film surface direction becomes preferable. From the above, the thickness of the resist layer made of a heat-reactive resist material is 10 nm or more and 100 nm or less, preferably 10 nm or more and 80 nm or less, more preferably 10 nm or more and 50 nm or less, and still more preferably 10 nm or more. It is 35 nm or less, most preferably 15 nm or more and 25 nm or less. By setting the thickness of the resist layer made of a heat-reactive resist material to the most preferable range of 15 nm or more and 25 nm or less, the amount of light absorbed by exposure or the like is moderate, and the heat in the film thickness direction and the film surface direction is uniform. There is an advantage of maintaining the nature. In addition, since the rate of change in the amount of light absorption with respect to the change in film thickness is small, even when film thickness unevenness occurs, heating unevenness is less likely to occur, and there is an advantage that a uniform pattern can be formed.

  The shape of the substrate according to the present embodiment can be a flat plate shape or a sleeve (roll, drum) shape. Many of the molds used for the master disk of an optical disc, nanoimprints, and the like are small and flat, and can be transferred by a simple device. On the other hand, the sleeve shape has a feature that a pattern can be transferred to a large area. In recent years, since there has been an increasing demand for forming a fine pattern in a large area, the shape of the substrate is preferably a sleeve shape.

  The material of the base material according to the present embodiment is not particularly limited. However, it is preferable that the material be excellent in surface smoothness and workability and be a material that can be dry-etched. Glass can be used as a representative of such materials. In addition, as the base material, silicon, silicon dioxide, or the like can also be used, and when performing dry etching, by providing a dry etching layer, aluminum, titanium, copper, silver, gold, or the like may be used as the base material. it can. Above all, from the viewpoint of the dry etching process, quartz glass is preferable as the substrate, and a desired aspect ratio can be formed only by controlling the time of the dry etching process.

  Next, the exposure step according to the present embodiment will be described. As a laser used for exposure, an excimer laser such as a KrF or ArF laser, a semiconductor laser, an electron beam, an X-ray, or the like can be used. Excimer lasers such as KrF and ArF lasers are very large and expensive, and electron beams, X-rays and the like require the use of a vacuum chamber, and therefore have considerable limitations in terms of cost and size. Therefore, it is preferable to use a semiconductor laser which can make the light source device very small 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, an excimer laser, or the like. However, the heat-reactive resist material according to the present embodiment is sufficient for a semiconductor laser. It is possible to form a fine pattern.

  The heat-reactive resist material according to the present embodiment preferably has both a region that thermally reacts and a region that does not thermally react within the laser spot diameter (within the irradiation range). In the present embodiment, not a photoresist material as a resist material, but by focusing on a heat-reactive resist material, the resist material has both a region where the resist material reacts and a region where the resist material does not react within a laser light irradiation range. Have achieved that. FIG. 4 is a schematic diagram showing the relationship between the spot diameter (irradiation area) of laser light and the temperature distribution within the spot diameter when the heat-reactive resist material is irradiated with laser light. As shown in FIG. 4, when the laser light is irradiated substantially perpendicularly to the main surface of the heat-reactive resist material, the spot diameter of the laser light is shifted from the focus of the laser light to the main surface of the resist material. Formed in a substantially circular shape. Here, as shown in the upper part of FIG. 4, the temperature distribution within the spot diameter of the laser light has a peak near the focal point of the laser light and decreases toward the outer peripheral edge of the irradiation range. In this case, by using a heat-reactive resist material that reacts at a predetermined temperature, the vicinity of the focal point of the laser beam can be exposed. That is, by making the heat-reactive resist material have a region that reacts at a predetermined temperature or more to the temperature distribution generated within the laser spot diameter, processing finer than the spot diameter can be realized. I have to. Thus, in the present embodiment, exposure can be performed using a semiconductor laser that is small, inexpensive, and does not require special auxiliary equipment. For example, the wavelength of a short wavelength semiconductor laser currently commercially available is about 405 nm, and its spot diameter is about 420 nm (numerical aperture: 0.85). For this reason, fine processing below 420 nm is impossible in principle as long as a photoresist material is used, but this limit can be exceeded by using a heat-reactive resist material, and fine processing below the wavelength of a semiconductor laser can be achieved. It can be performed.

  Next, the developing process according to the present embodiment will be described. The developing step is a step of selectively removing a portion that has been thermally transformed or a portion that has not been thermally transformed in the exposure step, and wet etching or dry etching can be used for the removal. From the viewpoint of uniformity and cost, wet etching is preferable. As a developer that can be used in the development step, an acid solution, an alkali solution, a complexing agent, an organic solvent, and the like can be used alone or in appropriate combination. As the acid solution, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, oxalic acid, hydrofluoric acid, ammonium nitrate and 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 a salt thereof, glycine and the like can be used alone or as a mixed solution. Further, a potential adjuster such as hydrogen peroxide or manganese peroxide may be added to the developer. Further, a developing agent may be added to the developer to improve the developability. In the development step, first, development with an acid developer and then development with an alkali developer to achieve the desired development, or development with an alkali developer and then development with an acid developer to achieve the desired development To achieve. Alternatively, development over a plurality of stages may be performed. Note that development may not be necessary depending on the composition of the heat-reactive resist selected.

  The method for causing the developer to act on the heat-reactive resist layer is not particularly limited, and the heat-reactive resist layer may be immersed in the developer, or the developer may be sprayed on the heat-reactive resist layer. By circulating the liquid when immersing the heat-reactive resist layer in the developer, or by operating the heat-reactive resist layer, by increasing the amount of liquid that touches the heat-reactive resist layer per unit time, The development speed can be increased. In addition, the developing speed can be increased by increasing the injection pressure when injecting the developer into the heat-reactive resist layer. When the developer is sprayed on the heat-reactive resist layer, a method of moving the nozzle, a method of rotating the heat-reactive resist layer, or the like can be used alone, but it is preferable to use them in combination because development proceeds uniformly. Any type of nozzle can be used for the jetting, and examples thereof include a line slit, a full cone nozzle, a hollow cone nozzle, a flat nozzle, a uniform flat nozzle, and a solid nozzle. It can be selected according to the shape of the material. Further, a one-fluid nozzle or a two-fluid nozzle may be used.

  When the developer is allowed to act on the heat-reactive resist layer, impurities such as insoluble fine powder present in the developer may cause unevenness particularly when developing fine patterns. Is preferably filtered in advance. The material of the filter used for filtration can be arbitrarily selected as long as it does not react with the developing solution, and examples thereof include PFA and PTFE. The coarseness of the filter may be selected according to the degree of fineness of the pattern, but is preferably 0.2 μm or less, more preferably 0.1 μm or less. In addition, in order to prevent precipitation and reattachment of the eluted components, it is preferable to spray the solution rather than immersion. Further, when spraying the developer onto the heat-reactive resist layer, it is desirable to dispose of the developer. When the developer is reused, it is preferable to remove the eluted components.

  The developing method preferably includes a step of cleaning the heat-reactive resist layer and a step of cleaning the developed substrate and the heat-reactive resist layer.

Next, the dry etching process according to the present embodiment will be described. The apparatus used for the dry etching treatment is not particularly limited as long as a fluorocarbon-based gas can be introduced in a vacuum, plasma can be formed, and the etching treatment can be performed. For example, a commercially available dry etching apparatus, RIE apparatus , An ICP device or the like can be used. The gas type, time, power, and the like for performing the dry etching process can be appropriately determined depending on the type of the heat-reactive resist, the type, thickness, etching rate, and the like of the first heat conductive layer (etching layer). The fluorocarbon-based gas used for the dry etching treatment is not particularly limited, but is CF ₄ , CHF ₃ , CH ₂ F ₂ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₆ , C ₄ F ₈ , C ₄ F. Fluorocarbons such as ₁₀ , C ₅ F ₁₀ , SF ₆ , and CCl ₂ F ₂ may be used, and may be used alone or as a mixture of a plurality of gases. Further, a gas obtained by mixing these gases with O ₂ , H ₂ , Ar, N ₂ , CO, etc., or HBr, NF ₃ , SF ₆ , CF ₃ Br, HCl, HI, BBr ₃ , BCl ₃ , Cl ₂ , SiCl The mixed gas of No. ₄ and a gas obtained by mixing them with a gas such as Ar, O ₂ , H ₂ , N ₂ , and CO are also included in the range of the CFC-based gas.

  Further, by optimizing the conditions such as the type, composition, etching pressure and temperature of the etching gas, the resistance of the resist mask and the etching direction of the base material and the etching layer can be controlled. For example, by adding Ar to a chlorofluorocarbon-based etching gas, the degree of dissociation of the chlorofluorocarbon-based gas is controlled to increase or decrease the etching rate of the base material, the etching layer, and the heat-reactive resist layer. And a method of manufacturing a desired mold shape by controlling the molar ratio between C and C or controlling the pressure of the dry etching process to control the etching direction from vertical to oblique.

  Finally, in the manufacturing process of the mold, it is necessary to remove the heat-reactive resist material. The method for removing the heat-reactive resist material is not particularly limited as long as it does not affect the base material and the etching layer. For example, wet etching, dry etching, or the like can be used.

  In the present embodiment, by using these mold manufacturing methods, a mold having a fine pattern with a pitch of 1 nm or more and 1 μm or less can be manufactured. The fine pattern according to this embodiment has a pitch of 1 nm to 5 μm, preferably 1 nm to 3 μm, more preferably 1 nm to 1 μm, further preferably 10 nm to 950 nm, and most preferably 30 nm to 800 nm.

  In this embodiment, LER can be set to 1.5 nm or less. The LER (Line Edge Roughness) is an index indicating the disorder of the pattern. Specifically, it is an index indicating how much the pattern side wall is uneven compared to the reference line. In this embodiment mode, the base material (or the dry etching layer) is dry-etched using the resist pattern as a mask to transfer the pattern to the base material. At that time, the pattern roughness of the resist is faithfully transferred to the substrate side through dry etching. From the above, the roughness of the resist affects the roughness of the base material. Accordingly, the LER of the fine pattern formed on the base material constituting the mold is 1.5 nm or less, and the fine pattern of the resist layer or the dry etching layer as a mask used for forming the fine pattern on the base material is used. LER is also required to be 1.5 nm or less.

  Here, the fine pattern will be described with reference to FIG. FIG. 5 is a cross-sectional view showing a manufacturing process of the fine pattern. FIG. 5A is a cross-sectional view showing a fine pattern including a base material 51 and a resist 52. Next, FIG. 5B shows a substrate 51 (a dry etching layer can be used instead of the substrate, using a fine pattern made of the resist 52 as a mask. FIG. 4 is a cross-sectional view showing a fine pattern 54 composed of a resist 52 and a base material 53, obtained by dry-etching (described) and transferring the fine pattern to the base material. Finally, FIG. 5C is a cross-sectional view showing a fine pattern made of the base material 53 from which the resist 52 has been removed.

  By using the resist composition of this embodiment, the LER can be reduced to 1.5 nm or less in all the fine patterns described above.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples implemented to clarify the effects of the present invention. In addition, this invention is not limited at all by the following Examples.

(LER)
The LER (Line Edge Roughness) is an index indicating the disorder of the pattern, and represents the roughness of the pattern edge shape, that is, the size of the unevenness formed at the pattern end. The smaller the value of LER, the less variation in the pattern shape. The LER was obtained by observing the surface of the developed resist by SEM (scanning electron microscope), and deriving the obtained image according to SEMI P47-0307 described in SEMI International Standards.

(Examples 1 to 6)
On a quartz glass substrate having a thickness of 2 inches and a thickness of 0.5 mm, heat was applied by changing sputtering conditions as shown in Table 2 using a sputtering method to change the density of a heat-reactive resist material containing copper (I) oxide as a main component. A reactive resist material was deposited to a thickness of 20 nm. The density of the heat-reactive resist material containing copper (I) oxide as a main component was determined by XRR analysis, and the values shown in Table 2 were obtained. In addition, the numerical value in the parenthesis in the column of the additive amount of the additive indicates the additive amount (mol%) of the additive to Cu.

The heat-reactive resist layer formed as described above 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: 60 nm to 800 nm
Exposure speed: 0.6 m / s to 11.0 m / s

  By modulating the intensity of the laser during exposure, various shapes and patterns can be produced. In experiments, a continuous groove was used as the pattern to confirm the exposure accuracy. The shape to be formed may be an isolated circular or elliptical shape depending on the intended use, and this embodiment is not limited at all by the exposure shape. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure.

  Subsequently, the heat-reactive resist layer exposed by the exposure machine was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

  Observation of the surface shape of the thus-developed heat-reactive resist layer with a scanning electron microscope (SEM) showed that the particle size and LER shown in Table 2 were obtained, and very good roughness was obtained. Was.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. When the cross-sectional shape of a substrate obtained by removing only the heat-reactive resist from the substrate provided with these patterns was observed by SEM, good pattern roughness was observed.

  Using the patterned substrate obtained above as a mold, a UV curable resin of 5 μm was applied on a PET film having a thickness of 100 μm, pressed against the mold, and the surface shape of the mold was transferred to the PET film. When the cross-sectional shape of the PET film was observed with a SEM, a shape almost inverted from the mold was transferred onto the film.

(Examples 7 to 9)
Except that the materials listed in Table 2 were selected as the additives, the heat containing copper (I) as a main component was obtained by changing the sputtering conditions as shown in Table 2 using a sputtering method under the same conditions as in Example 1. A heat-reactive resist material was formed by changing the density of the reactive resist material. The density of the heat-reactive resist material containing copper (I) oxide as a main component was determined by XRR analysis, and the values shown in Table 2 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 1. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

  Observation of the surface shape of the thus developed heat-reactive resist layer by SEM showed that the particle diameter and LER shown in Table 2 were obtained, and very good roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. The dry etching was performed using SF ₆ / O ₂ (ratio 95%: 5%) as an etching gas, a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 1.5 minutes. When the cross-sectional shape of a substrate obtained by removing only the heat-reactive resist from the substrate provided with these patterns was observed by SEM, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV curable resin in the same manner as in Example 1. The shape almost inverted from the mold was transferred to the film. .

(Examples 10 and 11)
The material shown in Table 2 is selected as an additive on a quartz glass roll substrate having a diameter of 80 mm and a length of 400 mm, and as shown in Table 2, the type of additive and the amount of additive are changed to obtain copper (I) oxide. A heat-reactive resist material having a thickness of 15 nm was formed by changing the density of the heat-reactive resist material containing as a main component. The density of the heat-reactive resist material containing copper (I) oxide as a main component was determined by XRR analysis, and the values shown in Table 2 were obtained.

The heat-reactive resist material formed as described above 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: 60 nm to 800 nm
Rotation speed: 210 rpm to 1670 rpm

  By modulating the intensity of the laser during exposure, various shapes and patterns can be produced, but in experiments, the groove shape was used as a pattern to confirm the exposure accuracy. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure.

  Subsequently, the heat-reactive resist exposed by the exposure machine was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

  The surface shape of the thus developed heat-reactive resist layer was transferred to a film using a UV curable resin in the same manner as in Example 1, and the surface shape was observed with a SEM. The diameter and LER were obtained and very good roughness was shown.

Next, the quartz glass roll was etched by dry etching using the obtained heat-reactive resist as a mask. The dry etching was performed using CF ₄ / O ₂ (ratio 98%: 2%) as an etching gas, a processing gas pressure of 1 Pa, a processing power of 1000 W, and a processing time of 2 minutes. When only the heat-reactive resist was peeled off from the substrate provided with these patterns, the surface shape was transferred to a film using a UV curable resin in the same manner as in Example 1, and the cross-sectional shape was observed with an SEM. Pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV curable resin in the same manner as in Example 1. The shape almost inverted from the mold was transferred to the film. .

(Examples 12 to 19)
Except that the materials listed in Table 2 were selected as the additives, the heat containing copper (I) as a main component was obtained by changing the sputtering conditions as shown in Table 2 using a sputtering method under the same conditions as in Example 1. A heat-reactive resist material was formed by changing the density of the reactive resist material. The density of the heat-reactive resist material containing copper (I) oxide as a main component was determined by XRR analysis, and the values shown in Table 2 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 1. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

  Observation of the surface shape of the thus developed heat-reactive resist layer by SEM showed that the particle diameter and LER shown in Table 2 were obtained, and very good roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. The dry etching was performed using SF ₆ / O ₂ (ratio 95%: 5%) as an etching gas, a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 1.5 minutes. When the cross-sectional shape of a substrate obtained by removing only the heat-reactive resist from the substrate provided with these patterns was observed by SEM, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV curable resin in the same manner as in Example 1. The shape almost inverted from the mold was transferred to the film. .

(Comparative Example 1 and Comparative Example 2)
On a quartz glass substrate having a thickness of 2 inches and a thickness of 0.5 mm, a heat-reactive resist material having a density of copper oxide (I) changed to 20 nm by changing sputtering conditions as shown in Table 2 using a sputtering method. The density of copper (I) was determined by XRR analysis, and the values in Table 2 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 1. A continuous channel was used as the pattern. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

The surface shape of the heat-reactive resist layer thus developed was observed by SEM. As a result, the particle diameter and LER shown in Table 2 were obtained, and the roughness was poor as compared with the examples. In Comparative Example 1, it is considered that the density of the film was 6.07 g / cm ³ , the effect of heat transfer was large at the time of exposure, and the particle size was large, so that the pattern roughness was deteriorated. On the other hand, in Comparative Example 2, the density of the film was 4.00 g / cm ³ , and in addition to the large particle diameter, the number of voids was increased in the pattern portion, and the pattern roughness was deteriorated in a state where pores were formed.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. When only the heat-reactive resist was removed from the substrate provided with these patterns, the cross-sectional shape was observed by SEM. As a result, a pattern having poor roughness was observed as it was.

(Comparative Example 3 and Comparative Example 4)
Except that the materials described in Table 2 were selected as additives, the heat conditions containing copper (I) as a main component were obtained by changing the sputtering conditions as shown in Table 2 using a sputtering method under the same conditions as in Comparative Example 1. A heat-reactive resist material was formed by changing the density of the reactive resist material. The density of the heat-reactive resist material containing copper (I) oxide as a main component was determined by XRR analysis, and the values shown in Table 2 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 1. A continuous channel was used as the pattern. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

The surface shape of the thus developed heat-reactive resist layer was transferred to a film using a UV curable resin in the same manner as in Example 1, and the surface shape was observed with a SEM. The diameter and LER were obtained, and the roughness was poor as compared with the examples. In Comparative Example 3, it is considered that the density of the film was 6.07 g / cm ³ , the influence of heat transfer was large at the time of exposure, and the particle size was large, so that the pattern roughness was deteriorated. On the other hand, in Comparative Example 4, the density of the film was 3.75 g / cm ³ , and in addition to the large particle diameter, the number of voids was increased in the pattern portion, and the pattern roughness was deteriorated in a state where pores were formed.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. When only the heat-reactive resist was removed from the substrate provided with these patterns, the cross-sectional shape was observed by SEM. As a result, a pattern having poor roughness was observed as it was.

(Comparative Example 5)
On a quartz glass roll substrate having a diameter of 80 mm and a length of 400 mm, silicon oxide was selected as an additive, and the sputtering conditions were changed as shown in Table 2 using a sputtering method to change the heat mainly containing copper (I). A heat-reactive resist material having a different density was formed to a thickness of 20 nm. The density of the heat-reactive resist material containing copper (I) oxide as a main component was determined by XRR analysis, and the values shown in Table 2 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 10. A groove shape was used as a pattern. When the XRD analysis of the heat-reactive resist material after film formation and after exposure was separately performed, it was in an amorphous state after film formation and in a crystalline state after exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 2. The development time was 1 minute.

The surface shape of the heat-reactive resist layer thus developed was transferred to a film using a UV curable resin in the same manner as in Example 1, and the surface shape was observed with an SEM. Was 120 nm, an LER of the value shown in Table 2 was obtained, and the roughness was poor as compared with the examples. Since the density of the film was 4.00 g / cm ³ , the particle diameter was large, the number of voids was increased in the pattern portion, and the pattern roughness was degraded in the state of voids.

Next, the quartz glass roll was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 5 Pa, a processing power of 400 W, and a processing time of 6 minutes. Only the heat-reactive resist was peeled from the patterned substrate to obtain a mold. Next, 5 μm of a UV-curable resin was applied on a PET film having a thickness of 100 μm, pressed against the mold, and the surface shape of the mold was transferred to the PET film. When the cross-sectional shape of the PET film was observed with an SEM, a pattern with poor roughness was observed as it was.

  Comparing Example 1 to Example 19 with Comparative Example 1 to Comparative Example 5, the thermal reaction type resist material according to Example 1 to Example 19 has a small LER value and an excellent roughness pattern. It can be seen that it is possible to form an ultrafine pattern while maintaining the same.

(Example 20)
It consists of CuO _0.49 N _0.01 , CuO _0.4 N _0.1 , CuO _0.3 N _0.2 , CuO _0.2 N _0.3 and CuN _0.5 shown in Table 3 below. Thermal reaction type resist materials each containing the composition were prepared. Then, each heat-reactive resist material was formed into a film having a thickness of 20 nm on a quartz glass substrate having a diameter of 2 inches (in) and a thickness of 0.5 mm by a sputtering method. Each composition shown in Table 3 was identified by XPS. The density of each heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

The heat-reactive resist layer formed as described above 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: 60 nm to 800 nm
Exposure speed: 0.6 m / s to 11.0 m / s

  By modulating the intensity of the laser during exposure, various shapes and patterns can be produced. In experiments, a continuous groove was used as the pattern to confirm the exposure accuracy. The shape to be formed may be an isolated circular or elliptical shape depending on the intended use, and this embodiment is not limited at all by the exposure shape. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure.

  Subsequently, the heat-reactive resist layer exposed by the above exposure machine was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus developed heat-reactive resist layer with a scanning electron microscope (SEM) showed that the LER of the value shown in Table 3 was obtained and very good pattern roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. Only the heat-reactive resist layer was peeled off from the substrate provided with these patterns, and the cross-sectional shape was observed by SEM. As a result, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV-curable resin. As a result, the shape almost inverted from the mold was transferred onto the film.

(Example 21)
A film was formed under the same conditions as in Example 20 except that CuO _0.4 S _0.1 and CuO _0.4 Se _0.1 were selected as the compositions contained in the heat-reactive resist material. Each composition shown in Table 3 was identified by XPS. The density of each heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 20. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus developed heat-reactive resist layer by SEM showed that LER shown in Table 3 was obtained, and very good pattern roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. The dry etching was performed using SF ₆ / O ₂ (ratio 95%: 5%) as an etching gas, a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 1.5 minutes. Only the heat-reactive resist was peeled off from the substrate provided with these patterns, and the cross-sectional shape was observed by SEM. As a result, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV-curable resin. As a result, the shape almost inverted from the mold was transferred onto the film.

(Example 22)
A heat-reactive resist material containing a composition composed of CuO _0.5 N _0.15 and CuO _0.3 N _0.05 shown in Table 3 was prepared. Then, each heat-reactive resist material was formed into a film having a thickness of 15 nm on a quartz glass roll base material having a diameter of 80 mm and a length of 400 mm by using a sputtering method. Each composition shown in Table 3 was identified by XPS. The density of each heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

The heat-reactive resist material formed as described above 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: 60 nm to 800 nm
Rotation speed: 210-1670 rpm

  By modulating the intensity of the laser during exposure, various shapes and patterns can be produced, but in experiments, the groove shape was used as a pattern to confirm the exposure accuracy. The shape to be formed may be an isolated circular shape or an isolated elliptical shape depending on the intended use, and the present embodiment is not limited at all by the exposure shape. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure.

  Subsequently, the exposed heat-reactive resist was developed. The developer was used under the conditions shown in Table 3. The development time was 2 minutes.

  The surface of the substrate with the pattern obtained above was transferred to a film using a UV-curable resin. When the surface of the obtained film was observed with a SEM, a shape almost inverted from the mold was observed, and an LER of the value shown in Table 3 was obtained, showing very good pattern roughness.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. The dry etching was performed using CF ₄ / O ₂ (ratio 98%: 2%) as an etching gas, a processing gas pressure of 1 Pa, a processing power of 1000 W, and a processing time of 2 minutes. Using a substrate obtained by removing only the heat-reactive resist from the substrate provided with these patterns, the surface shape was transferred to a film using a UV curable resin. When the surface of the obtained film was observed with a SEM, a shape almost inverted from the mold was observed, and very good pattern roughness was exhibited.

(Example 23)
A film was formed under the same conditions as in Example 20 except that CuO _0.4 N _0.1 was selected as the composition contained in the heat-reactive resist material and SiO ₂ (8 mol%) was selected as the additive. The compositions shown in Table 3 were identified by XPS, and the added amount of SiO ₂ as an additive was identified by XRF (fluorescent X-ray). The density of the heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 20. When the XRD analysis of the heat-reactive resist material after film formation and after exposure was separately performed, it was in an amorphous state after film formation and in a crystalline state after exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus-developed heat-reactive resist layer by SEM showed that LER of the value shown in Table 3 was obtained, and very good pattern roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. Only the heat-reactive resist was peeled off from the substrate provided with these patterns, and the cross-sectional shape was observed by SEM. As a result, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV-curable resin. As a result, the shape almost inverted from the mold was transferred onto the film.

(Example 24)
A laminated material having the composition shown in Table 3 was formed. At this time, the average composition contained in the heat-reactive resist material was CuO _0.4 N _0.1 . The density of each heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

Further, as shown in Table 3, a heat-reactive resist material in which 8 mol% of SiO ₂ was added as an additive in addition to the above laminated material was also prepared. Specifically, CuO _0.5 is formed in a thickness of 10 nm on a quartz glass substrate having a thickness of 2 mm and a thickness of 0.5 mm by sputtering, and CuO _0.2 N _0.3 is formed thereon by sputtering. To form a layered material with a thickness of 5 nm. On the other hand, in the composition to which the additive was added, a composition in which CuO _0.5 and 8 mol% of SiO ₂ as an additive were added to a quartz glass substrate having a thickness of 2 inφ and a thickness of 0.5 mm was formed to a thickness of 10 nm by a sputtering method. A film was formed, and a composition in which CuO _0.2 N _0.3 and 8 mol% of SiO ₂ were added as an additive was formed thereon to a thickness of 5 nm by a sputtering method to obtain a laminated material. The compositions shown in Table 3 were identified by XPS and XRF.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 20. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus developed heat-reactive resist layer by SEM showed that LER shown in Table 3 was obtained, and very good pattern roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. Only the heat-reactive resist was peeled off from the substrate provided with these patterns, and the cross-sectional shape was observed by SEM. As a result, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV-curable resin. As a result, the shape almost inverted from the mold was transferred onto the film.

(Example 25)
As shown in Table 3, the composition was changed from CuO _{0.5 to} CuN _0.5 so that the composition ratio of O was gradually replaced by N in the film thickness direction. The average composition obtained at this time was CuO _0.25 N _0.25 shown in Table 3. Specifically, a film was formed on a quartz glass substrate having a thickness of 2 mm and a thickness of 0.5 mm by a sputtering method at the start of film formation under the condition that only argon and oxygen were used as process gases and nitrogen was not introduced. Then, the introduction amount of nitrogen was gradually increased and the introduction amount of oxygen was reduced, and at the end of the film formation, a film was formed under the condition of only argon and nitrogen, and a film having a thickness of 20 nm was formed. The compositions shown in Table 3 were identified by XPS. The density of the heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 20. When the XRD analysis of the heat-reactive resist material after film formation and after exposure was separately performed, it was in an amorphous state after film formation and in a crystalline state after exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus-developed heat-reactive resist layer by SEM showed that LER of the value shown in Table 3 was obtained, and very good pattern roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. When the cross-sectional shape of a substrate obtained by removing only the heat-reactive resist from the substrate provided with these patterns was observed by SEM, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV-curable resin. As a result, the shape almost inverted from the mold was transferred onto the film.

(Example 26)
Same as Example 20 except that CuO _0.4 N _0.1 was selected as the composition contained in the heat-reactive resist material and Na ₂ O (0.01 mol%) / SiO ₂ (8 mol%) was selected as the additive. Film formation was performed under the following conditions. The composition shown in Table 3 was identified by XPS, and the amount of Na ₂ O / SiO ₂ added as an additive was identified by XRF. The density of the heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 20. When the XRD analysis of the heat-reactive resist material after film formation and after exposure was separately performed, it was in an amorphous state after film formation and in a crystalline state after exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus-developed heat-reactive resist layer by SEM showed that LER of the value shown in Table 3 was obtained, and very good pattern roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. Only the heat-reactive resist was peeled off from the substrate provided with these patterns, and the cross-sectional shape was observed by SEM. As a result, good pattern roughness was observed.

  Using the substrate with a pattern obtained above as a mold, the surface shape was transferred to a film using a UV-curable resin. As a result, the shape almost inverted from the mold was transferred onto the film.

(Comparative Example 6)
A film was formed under the same conditions as in Example 20 except that CuO _0.8 N _0.2 and CuO _0.1 N _0.05 were selected as the compositions contained in the heat-reactive resist material. The composition was identified by XPS. The density of each heat-reactive resist material was determined by XRR analysis, and the values shown in Table 3 were obtained.

  The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 20. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure. Subsequently, the exposed heat-reactive resist layer was developed. The developer was used under the conditions shown in Table 3. The development time was 1 minute.

  Observation of the surface shape of the thus-developed heat-reactive resist layer by SEM showed that LER of the values shown in Table 3 was obtained, and the pattern roughness was poor as compared with the examples.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. Only the heat-reactive resist was peeled off from the substrate provided with these patterns, and the cross-sectional shape was observed by SEM. As a result, a pattern with poor roughness was observed as it was.

  Comparing Examples 20 to 26 with Comparative Example 6, it is possible to form a fine pattern while maintaining excellent pattern roughness by using the heat-reactive resist materials according to Examples 20 to 26. I understand.

Based on Example 20 to Example 26, were derived _CuO x _{A y} as a composition contained in the thermal reaction type resist material. At this time, A is at least one selected from N, S, and Se, and 0.35 ≦ x + y ≦ 0.65, 0 ≦ x, and 0 <y.

(Example 27)
Using a sputtering method, titanium oxide (IV), zirconium oxide (IV), hafnium oxide (IV), nickel oxide (II), and zinc oxide (II) were formed on a quartz glass substrate having a thickness of 2 inches and a thickness of 0.5 mm using a sputtering method. A heat-reactive resist material as a main component was deposited to a thickness of 20 nm.

The heat-reactive resist layer formed as described above 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: 60 nm to 800 nm
Exposure speed: 0.6 m / s to 11.0 m / s

  By modulating the laser intensity during exposure, various shapes and patterns can be produced. In experiments, a continuous groove was used as the pattern to confirm the exposure accuracy. The shape to be formed may be an isolated circular or elliptical shape depending on the intended use, and this embodiment is not limited at all by the exposure shape. Separately, when XRD analysis was performed on each of the heat-reactive resist materials after film formation and after exposure, they were in an amorphous state after the film formation and in a crystalline state after the exposure.

  Subsequently, the heat-reactive resist layer exposed by the exposure machine was developed. The developer was used under the conditions shown in Table 4.

  Observation of the surface shape of the thus developed heat-reactive resist layer by SEM (scanning electron microscope) revealed that LER having the value shown in Table 4 was obtained, and very good roughness was exhibited.

Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. When the cross-sectional shape of a substrate obtained by removing only the heat-reactive resist from the substrate provided with these patterns was observed by SEM, good pattern roughness was observed.

  Using the patterned substrate obtained above as a mold, a UV curable resin of 5 μm was applied on a PET film having a thickness of 100 μm, pressed against the mold, and the surface shape of the mold was transferred to the PET film. When the cross-sectional shape of the PET film was observed with a SEM, a shape almost inverted from the mold was transferred onto the film.

(Comparative Example 7)
On a quartz glass substrate having a thickness of 2 inches and a thickness of 0.5 mm, a resist material containing titanium aluminum, nickel tin, and germanium selenium as main components was deposited to a thickness of 20 nm by a sputtering method.

The heat-reactive resist layer formed as described above was exposed under the same conditions as in Example 27. A continuous channel was used as the pattern. Separately, XRD analysis was performed on each heat-reactive resist material after film formation and after exposure, and it was found that germanium selenium was in an amorphous state and after exposure was in a crystalline state. On the other hand, titanium aluminum and nickel tin could not be used as a phase change mode resist material in a crystalline state after film formation. Subsequently, the exposed heat-reactive resist layer was developed with respect to germanium selenium. The developer was used under the conditions shown in Table 4. Next, the quartz glass substrate was etched by dry etching using the obtained heat-reactive resist as a mask. Dry etching was performed using SF ₆ as an etching gas, under the conditions of a processing gas pressure of 1 Pa, a processing power of 300 W, and a processing time of 2 minutes. After dry etching, the pattern was not observed when observed by SEM. Since the boiling points of the fluorides of the elements constituting germanium selenium are all 200 ° C. or less (Ge: −36 ° C., Se: 106 ° C.), the dry etching resistance is poor, and the resist material functions as a mask during dry etching. Probably because they did not.

  Comparing Example 27 with Comparative Example 7, it was found that the use of the heat-reactive resist material according to Example 27 allowed formation of a fine pattern while maintaining excellent pattern roughness.

  The heat-reactive resist material according to the present invention is particularly useful as a mold mask for transferring an ultrafine pattern.

Claims (14)

A resist material made of amorphous oxide, which forms a pattern using a phase change mode that changes from amorphous to crystalline,
A thermally reactive resist material comprising, as the amorphous oxide, a composition of the formula (1) in which part or all of oxygen of copper (I) oxide is replaced by element A.
CuO _x A _y (1)
Here, A is at least one selected from N, S, and Se, and 0.35 ≦ x + y ≦ 0.65, 0 ≦ x, and 0 <y. Further, x and y indicate the atomic ratio, and in the formula (1), the atomic ratio of Cu: O: A is set to 1: x: y.   Along with the composition, at least one of Na, Mg, Si, Sr, V, Cr, Mo, W, Ag, Zn, Ga, Ge, Nb, Ta and oxides, nitrides, and oxynitrides thereof The heat-reactive resist material according to claim 1, wherein is contained as an additive.   The heat-reactive resist material according to claim 2, wherein at least one of Si and its oxide, nitride, and oxynitride is contained as an additive together with the composition.   4. The heat-reactive resist material according to claim 1, wherein the element A is N and satisfies 0.35 ≦ x + y ≦ 0.65, 0 ≦ x, and 0 <y. . A method for producing a mold having an uneven shape on the surface of a substrate, using the heat-reactive resist material according to claim 1.
A step (1) of forming a heat-reactive resist layer on the base material using the heat-reactive resist material;
After exposing the heat-reactive resist layer, developing with a developer (2);
(3) dry-etching the base material with a chlorofluorocarbon-based gas using the heat-reactive resist layer as a mask;
Removing (4) the heat-reactive resist layer;
A method for manufacturing a mold, comprising:   The method according to claim 5, wherein the heat-reactive resist layer is formed to have a thickness of 10 nm or more and 100 nm or less.   The method according to claim 5, wherein the heat-reactive resist layer is formed by any one of a sputtering method, an evaporation method, and a CVD method.   The method for manufacturing a mold according to any one of claims 5 to 7, wherein the substrate has a flat plate shape.   The method for manufacturing a mold according to claim 5, wherein the substrate has a sleeve shape.   The method according to any one of claims 5 to 9, wherein the base material is quartz glass.   The method according to claim 5, wherein the exposure in the step (2) is performed using a semiconductor laser.   A mold manufactured by the method for manufacturing a mold according to claim 5.   The mold according to claim 12, wherein the mold has a concavo-convex shape formed of a fine pattern having a pitch of 1 nm or more and 1 μm or less.   14. The mold according to claim 12, wherein LER is 1.5 nm or less.

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