JP4696132B2 - Resist material and electron beam recording resist material - Google Patents

Description

  The present invention relates to a resist material and an electron beam recording resist material capable of forming a clear and fine pattern with less exposure, a resist substrate and an electron beam recording resist substrate using the same, and a method for producing a pattern forming body It is about.

  Conventionally, organic resist materials have been mainly used for microfabrication of optical devices, magnetic devices, semiconductor devices and the like. Organic resist materials are versatile and widely used in the field of photolithography. However, since the molecular weight is high, there is a problem that the pattern at the boundary between the exposed portion and the unexposed portion tends to be unclear. there were. In addition, since direct recording is performed with light or an electron beam, it is difficult to form a fine pattern smaller than the spot diameter of the light or electron beam.

  On the other hand, since the inorganic resist material has a low molecular weight, it has an advantage that the pattern of the boundary portion between the exposed portion and the unexposed portion is clear. Therefore, various studies are currently being conducted. For example, Patent Document 1 describes a method for selectively removing a portion of a specific crystal state of a chalcogen compound using an etching rate difference due to a difference in crystal state of the chalcogen compound to obtain an optical information recording medium master. Yes.

  In Patent Document 1, a method of changing the crystal state of the chalcogen compound by heat generated by light exposure or the like is used, and such a method is a method called heat mode recording. In heat mode recording, only the part that has reached a temperature above a certain threshold undergoes a change in physical and chemical state, and the part that does not reach the threshold changes even if the temperature rises. Since it does not occur, there is an advantage that a clear pattern is formed. Furthermore, in heat mode recording, only the part that reaches the temperature above the threshold among the parts exposed by light or electron beam causes a change in state, so a fine pattern smaller than the spot diameter of light or electron beam is formed. Has the advantage of being able to.

  Further, Patent Document 2 discloses a method for manufacturing a master of an optical information recording medium using heat mode recording. By providing a recording auxiliary layer in addition to a resist film, recording sensitivity is improved and etching after recording is performed. It is stated that there is an effect of controlling the shape.

  On the other hand, Patent Document 3 discloses a resist material using an incomplete oxide of a transition metal such as W or Mo as a resist film. In Patent Document 3, the incomplete oxide utilizes the absorption of ultraviolet rays and visible light, and aims to obtain a fine pattern using an existing exposure apparatus.

  However, any of the resist materials described in Patent Documents 1 to 3 has a problem that the sensitivity to light and electron beams tends to be insufficient due to its high decomposition temperature. In addition, from the viewpoint of improving the recording sensitivity, Patent Document 2 discusses a method of providing a recording auxiliary layer. However, the provision of the recording auxiliary layer has a problem that causes an increase in process and a complicated layer structure. It was.

  In addition, when recording with an electron beam, the electron beam penetrates to the substrate side without reacting with the resist material, or a material such as a metal having conductivity is provided on the substrate or the upper surface of the substrate in order to avoid charge of electrons. There is another problem such as necessity, but the countermeasures are not clearly described in the prior art.

Japanese Patent Laid-Open No. 10-97738 JP 2005-11489 A JP 2003-315988 A

  From the above, it is desired to provide a resist material and an electron beam recording resist material that have high sensitivity to light and an electron beam and can form a clear and fine pattern with less exposure.

The present invention is a resist substrate having a substrate and a resist film formed on the substrate and using a resist material, the resist material having a metal compound, and a metal constituting the metal compound The element is a Group 14 or Group 15 metal element, the metal compound is a metal oxide, the metal compound is a stoichiometrically incomplete compound, and the metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, X is a composition ratio of O in the metal compound), and X in the metal compound is 75%, X in the metal compound is 75. % To 95%, and an electron beam moderation layer is formed on the resist film.

The present invention also includes a metal compound, wherein the metal element constituting the metal compound is a Group 14 or Group 15 metal element, the metal compound is a metal oxide, and the metal compound is a stoichiometric amount. The above-mentioned metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, and X is a composition ratio of O in the metal compound). When X is 100%, a resist film using a resist material in which X in the metal compound is in the range of 75% to 95% is formed on a substrate, and an electron beam is formed on the resist film. Provided is a method for producing a pattern forming body, wherein after forming a deceleration layer, the resist film is irradiated with an electron beam.

  Hereinafter, the resist material, the resist substrate, the electron beam recording resist material, the electron beam recording resist substrate, and the method for producing the pattern forming body of the present invention will be described in detail.

A. Resist Material First, the resist material of the present invention will be described. The resist material of the present invention is a resist material having a stoichiometrically incomplete metal compound. In the present invention, the “stoichiometrically incomplete metal compound” is defined as a compound in which the composition ratio of the metal element and the nonmetal element bonded to the metal element is not stoichiometrically matched. Conversely, a metal compound in which the composition ratio of the metal element and the nonmetal element is stoichiometrically matched is defined as “stoichiometrically complete metal compound”.

For example, when the metal oxide Bi ₂ O ₃ is considered as the metal compound, the composition ratio is converted to Bi _1-X O _{X. When} X = 0.6, “stoichiometrically complete metal oxide” It can be said that when X = 0.6, it is a “stoichiometrically incomplete metal oxide”. In general, the composition ratio of the nonmetallic element does not exceed the ideal composition ratio of the nonmetallic element determined by the valence of the metal element. Specifically, in the above example, X does not normally exceed 0.6, and X falls within the range of 0 <X <0.6.

  Also, depending on the metal element, there is a metal element that can take a plurality of valences, and may form metal compounds having different valences, but if the composition proportions do not stoichiometrically match, It can be treated as “stoichiometrically incomplete metal oxide”. The valence of the metal element in the metal oxide can be analyzed with a commercially available analyzer.

  Moreover, the resist material of this invention can be divided roughly into the following two aspects according to the kind of metal compound used. That is, the metal element constituting the metal compound is a group 14 or 15 metal element (first aspect) and the metal compound is a metal nitride. This is an embodiment (second embodiment). Hereinafter, the two aspects will be described in detail.

1. First Aspect First, the resist material according to the first aspect of the present invention will be described. The resist material of this aspect is a resist material having a metal compound, wherein the metal element constituting the metal compound is a Group 14 or Group 15 metal element, and the metal compound is stoichiometric. It is characterized by being an incomplete compound.

  According to this aspect, by using a metal compound containing a Group 14 or Group 15 metal element, a resist material capable of forming a clear and fine pattern with less exposure can be obtained. This is due to the fact that the decomposition temperature of the metal compound containing a Group 14 or Group 15 metal element is lower than the decomposition temperature of the metal compound containing a transition metal element used in conventional resist materials. It is. Note that the decomposition temperature of the metal compound is a temperature at which the bond of the metal compound is released only by thermal energy when the temperature exceeds that temperature, and almost coincides with the melting point in most metal compounds, but in a compound having a lower sublimation temperature. Match the sublimation point. That is, in conventional resist materials using transition metal elements, since the decomposition temperature of the transition metal elements is high, the sensitivity to light and electron beams is low, and many exposures are necessary to obtain a desired pattern. . In contrast, since the resist material of this embodiment has a low decomposition temperature, it has high sensitivity to light and electron beams, and can form a clear pattern with less exposure.

Next, application examples of the resist material of this embodiment will be described with reference to the drawings. For example, as shown in FIG. 1A, a member having a substrate 1 and a resist film 2 made of a resist material Bi ₂ O _{3 -α} is prepared. Next, as shown in FIG. 1B, only a portion heated to a temperature equal to or higher than a predetermined threshold value is decomposed into Bi ₂ O _3-β and O ₂ by exposure with light or an electron beam. Part 3 is formed. At this time, it is considered that the recording unit 3 forms a porous structure due to the elimination of O ₂ . Further, among the portions exposed to light or electron beam, only the portion that reaches a temperature equal to or higher than a predetermined threshold value becomes the recording unit 3, so that a fine pattern smaller than the spot diameter of the light or electron beam can be formed. it can. On the other hand, the portion that has not reached the temperature equal to or higher than the predetermined threshold value does not undergo a decomposition reaction or the like even if the temperature is raised, and becomes the unrecorded portion 4 as it is. Further, the crystal state or the like of the recording unit 3 is different from the crystal state or the like of the non-recorded unit 4, and the solubility in the developer changes, so that only the recording unit 3 is removed as shown in FIG. be able to.

Next, the metal compound used in this embodiment will be described. Here, the metal compound used in this embodiment is defined as M _1-X A _X (M is a metal element, A is a nonmetal element, and X is a composition ratio of A in the metal compound). .

  The M may represent a single metal element or may represent a plurality of metal elements. When M represents a single metal element, the M is not particularly limited as long as it is a Group 14 or Group 15 metal element. Specifically, Si, Ge, Sn, Pb, As, Sb, and Bi can be mentioned, and Bi, Sn, and Ge are particularly preferable.

  In addition, when M represents a plurality of metal elements, the M is not particularly limited as long as it has at least a Group 14 or Group 15 metal element. Examples thereof include those having a plurality of group or group 15 metal elements, those having a group 14 or group 15 metal element, and other metal elements. At this time, the group 14 or group 15 metal element is preferably Bi, Sn, or Ge. Among these, in this embodiment, the M is at least one selected from the group consisting of at least one metal element selected from the group consisting of Bi, Sn, and Ge, and Si, Cu, Fe, Ti, and Al. It is preferable to have more than one kind of metal element. This is because a resist material capable of forming a clear and fine pattern can be obtained. Moreover, said M becomes a metal compound from which decomposition temperature differs in combination with A mentioned later. Therefore, in the present invention, it is preferable to appropriately select A, which will be described later, so that a compound of A and at least one metal element of M is a metal compound having a lower decomposition temperature.

  Specific examples of A include O, N, C, etc. Among them, O and N are preferable, and N is particularly preferable. A resist material capable of obtaining a clear pattern with less exposure can be obtained. When A is O, a metal oxide is formed. When A is N, a metal nitride is formed. When A is C, a metal carbide is formed. That is, examples of the metal compound include metal oxides, metal nitrides, metal carbides, and the like, among which metal oxides and metal nitrides are preferable, and metal nitrides are particularly preferable.

  The range of X is not particularly limited because it varies greatly depending on the application of the resist material. However, the lower the composition ratio of non-metallic elements (for example, nitrogen), the stronger the metal properties, and the higher the light absorption, but the higher the thermal conductivity, the heat does not stay and the sensitivity decreases. It is necessary to keep in mind. Conversely, the higher the proportion composition of non-metallic elements (for example, nitrogen), the closer to the stoichiometrically perfect metal compound (for example, nitride), the improvement in light absorption was not observed, and ultraviolet light or visible light was used. It should be noted that exposure may be difficult.

  When the value of X was examined in detail, when X, which is the stoichiometric composition ratio, was 100%, it was found that X was in the range of 75% to 95% in terms of the balance between light absorption and heat conduction. It was desirable. In addition, when recording with an electron beam, since light absorptivity does not need to be considered, what is necessary is just a compound necessary and sufficient for reaction. Therefore, it may be closer to a stoichiometrically perfect metal compound (for example, nitride) than a recording using light, or may be a perfect metal compound (for example, nitride). That is, X is desirably in the range of 75% to 100%.

  Further, the melting point of the metal compound used in this embodiment is not particularly limited, but specifically, it is in the range of 0 ° C. to 1500 ° C., particularly in the range of 100 ° C. to 1200 ° C., particularly 200 ° C. It is preferable to be within a range of ˜1000 ° C. This is because when the melting point is higher than the above range, the sensitivity to light or electron beam tends to be insufficient, and when the melting point is lower than the above range, the stability of the metal compound is deteriorated. Further, from the viewpoint of the stability of the metal compound at room temperature, the melting point of the metal compound is preferably 200 ° C. or higher. Table 1 shows an example of the melting points of Group 14 or Group 15 metal compounds and transition metal compounds. As is apparent from Table 1, the melting point of the Group 14 or Group 15 metal compound is generally lower than that of the transition metal compound.

Moreover, the resist material of this aspect may contain the heat generating agent which converts light and an electron beam into heat. Such a heat generating agent is not particularly limited, and specific examples include noble metals such as Pd, Ag, Au, and Pt. In addition, halogen elements having high electron affinity such as F, Cl, Br, and I, and metal halides such as LiF, NaCl, KBr, CaF ₂ , MgF ₂ , AlF ₃ , and BiF ₃ are also effective in converting an electron beam into heat. Therefore, it is effective to contain it in a resist material.

  In addition, the application of the resist material of the present embodiment is not particularly limited, but can be used for optical devices, magnetic devices, semiconductor devices, and the like. Further, the resist material of this embodiment may be an electron beam recording resist material or an optical recording resist material, but among them, an electron beam recording resist material is preferable. This is because a finer pattern can be formed.

  Further, the method for producing the resist material of the present embodiment is not particularly limited as long as it is a method capable of obtaining a resist material capable of forming a clear and fine pattern with less exposure. Can include reactive sputtering, vapor deposition, and the like. As an example of a method for producing a resist material using a reactive sputtering method, a sputtering target made of a group 14 or group 15 metal alone is used, and sputtering is performed in an argon and oxygen atmosphere to achieve a stoichiometric amount. And a method for obtaining a resist material having an incomplete metal oxide. At this time, the oxygen composition ratio in the metal oxide can be controlled by changing the oxygen concentration. Further, a metal oxide having a plurality of metal elements can be obtained by using a sputtering target having a plurality of metal elements. In addition, when a stoichiometrically incomplete metal nitride is obtained, the reactive sputtering method may be similarly performed in an argon and nitrogen atmosphere.

2. Second Aspect Next, the resist material according to the second aspect of the present invention will be described. The resist material of this embodiment is a resist material having a metal compound, wherein the metal compound is a metal nitride, and the metal compound is a stoichiometrically incomplete compound. It is.

  According to this aspect, by using the metal nitride, a resist material capable of forming a clear pattern with less exposure can be obtained. This is because the decomposition temperature of the metal nitride is lower than the decomposition temperature of the metal oxide or the like used in the conventional resist material.

Next, application examples of the resist material of this embodiment will be described with reference to the drawings. For example, as shown in FIG. 2A, a member having a substrate 1 and a resist film 2 made of a resist material BiN _1-α is prepared. Next, as shown in FIG. 2B, only a portion heated to a temperature equal to or higher than a predetermined threshold is decomposed into BiN _1-β and N ₂ by exposure with light or an electron beam, and the recording unit 3 Is formed. At this time, it is considered that the recording unit 3 forms a porous structure by removing N ₂ . Further, among the portions exposed to light or electron beam, only the portion that reaches a temperature equal to or higher than a predetermined threshold value becomes the recording unit 3, so that a fine pattern smaller than the spot diameter of the light or electron beam can be formed. it can. On the other hand, the portion that has not reached the temperature equal to or higher than the predetermined threshold value does not undergo a decomposition reaction or the like even if the temperature is raised, and becomes the unrecorded portion 4 as it is. Further, the crystal state or the like of the recording part 3 is different from the crystal state or the like of the unrecorded part 4, and the solubility in the developer changes, so that only the recording part 3 is removed as shown in FIG. be able to.

Next, the metal compound used in this embodiment will be described. Here, the metal compound used in this embodiment is defined as M _1-X N _X (M represents a metal element, N represents a nitrogen element, and X represents a composition ratio of N in the metal nitride). .

  The M may represent a single metal element or may represent a plurality of metal elements. When M represents a single metal element, M is not particularly limited as long as it is a metal element capable of forming a metal nitride. The metal element is preferable, and among the group 14 or 15 metal elements, Bi, Sn, and Ge are preferable.

  Further, when M represents a plurality of metal elements, M is not particularly limited as long as it is a combination of metal elements capable of forming a metal nitride. Alternatively, those having a Group 15 metal element can be given. In such a case, as M, those having a plurality of group 14 or group 15 metal elements, those having a group 14 or group 15 metal element, and other metal elements, etc. Can be mentioned. At this time, the group 14 or group 15 metal element is preferably Bi, Sn, or Ge. Among these, in this embodiment, the M is at least one selected from the group consisting of at least one metal element selected from the group consisting of Bi and Sn, and Ge, Si, Cu, Fe, Ti, and Al. It is preferable to have more than one kind of metal element. This is because a resist material capable of forming a clear and fine pattern can be obtained.

  The range of X is not particularly limited because it varies greatly depending on the application of the resist material. However, it should be noted that the lower the composition ratio of the nitrogen element, the stronger the metal properties of the metal nitride, and the light absorption increases, but the thermal conductivity also increases and heat does not stay and the sensitivity decreases. is there. Conversely, the higher the nitrogen composition, the closer to the stoichiometrically complete metal nitride, no improvement in light absorption, and exposure using ultraviolet or visible light may be difficult. It is necessary to keep in mind.

  When the value of X was examined in detail, when X, which is the stoichiometric composition ratio, was 100%, it was found that X was in the range of 75% to 95% in terms of the balance between light absorption and heat conduction. It was desirable. In addition, when recording with an electron beam, since light absorptivity does not need to be considered, what is necessary is just a compound necessary and sufficient for reaction. Therefore, it may be closer to the stoichiometric complete metal nitride than the recording using light, or it may be a complete metal nitride. That is, X is desirably in the range of 75% to 100%.

  Further, the melting point of the metal nitride used in this embodiment is not particularly limited, but specifically, it is in the range of 0 ° C. to 1500 ° C., particularly in the range of 100 ° C. to 1000 ° C., particularly 200 It is preferable to be within the range of from ℃ to 400 ℃. When the melting point is higher than the above range, the sensitivity to light or electron beam tends to be insufficient, and when the melting point is lower than the above range, the stability of the metal nitride is poor, which is not preferable. Further, from the viewpoint of the stability of the metal nitride at normal temperature, the melting point of the metal nitride is preferably 200 ° C. or higher. Table 2 shows an example of melting points of metal nitrides and metal oxides. As is apparent from Table 2, the melting point of the metal nitride is generally lower than that of the metal oxide.

  Moreover, the resist material of this aspect may contain the heat generating agent which converts light and an electron beam into heat. Such an exothermic agent is the same as that described in the first aspect, and thus the description thereof is omitted here. Further, the use and manufacturing method of the resist material of the present embodiment are also the same as those described in the first embodiment, and thus the description thereof is omitted here.

B. Next, the resist substrate of the present invention will be described. The resist substrate of the present invention includes a substrate and a resist film formed on the substrate and using the above-described resist material.

  According to the present invention, since the resist film using the resist material described above is provided, there is an advantage that a clear and fine pattern can be formed with less exposure.

  As the substrate used in the present invention, the same substrate as that used for a general resist substrate can be used. Further, the resist material used in the present invention is the same as that described in “A. Resist material”, and therefore, the description thereof is omitted here. Examples of a method for forming a resist film on the substrate include a reactive sputtering method and a vapor deposition method.

  In the present invention, the substrate is preferably a metal substrate, and a heat storage layer is preferably formed between the metal substrate and the resist film. This is because the provision of the heat storage layer has an advantage that heat is maintained in heat mode recording even when a metal substrate having high thermal conductivity is used. The heat storage layer is a layer that may be omitted when a substrate having a low thermal conductivity such as a glass substrate or a resin substrate and having a heat storage property is used.

  FIG. 3 is a schematic cross-sectional view showing an example of a resist substrate having a heat storage layer. The resist substrate shown in FIG. 3 has a metal substrate 1 ′, a heat storage layer 5 formed on the metal substrate 1 ′, and a resist film 2 formed on the heat storage layer 5.

  The material of the metal substrate is not particularly limited as long as it has a high thermal conductivity, and examples thereof include metal plates such as silicon and aluminum.

The material for the heat storage layer is not particularly limited as long as it can retain heat. For example, a metal nitride, metal oxide, metal carbide, metal sulfide having a low thermal conductivity, Examples thereof include metal compounds such as metal selenides, and mixtures thereof. Among them, a dielectric material using a metal different from the metal compound used for the resist film is preferable, and ZnS—SiO ₂ is particularly preferable. A resin material can also be used for the heat storage layer.

  In particular, when recording with an electron beam, it is necessary to provide a highly conductive material such as a metal on the substrate or the upper surface of the substrate in order to prevent electrons from being charged on the substrate and affecting the electron beam. Therefore, the heat storage layer is effective for achieving both high conductivity and low thermal conductivity.

  Although it does not specifically limit as thickness of the said thermal storage layer, For example, it is desirable to exist in the range of 10 nm-1000 nm, especially the range of 20 nm-400 nm. If it is too thin, the effect of heat storage will be insufficient, and if it is too thick, productivity will be lowered, and the surface property of the film will be deteriorated, and peeling and cracking due to the stress of the film will be caused.

  The method for forming the heat storage layer is not particularly limited as long as it is a method capable of obtaining the heat storage layer described above. Specifically, when the material of the heat storage layer is the above-described metal compound or the like, for example, a sputtering method, a vapor deposition method, or the like can be given.

  In the present invention, when recording with an electron beam, an electron beam moderation layer is preferably formed on the resist film. This is because by providing the electron beam deceleration layer, many electrons react with the resist film, and the electron beam can be efficiently converted into heat. The electron beam decelerating layer will be described in detail in “D. Resist material for electron beam recording” described later, and the description thereof is omitted here.

C. Next, the resist material for electron beam recording of the present invention will be described. The resist material for electron beam recording of the present invention is used for electron beam recording, and can be roughly divided into the following two modes depending on the type of metal compound. That is, the metal element constituting the metal compound is a group 14 or group 15 metal element (third aspect), and the metal compound is a metal nitride, This is the fourth mode. Hereinafter, the two aspects will be described in detail.

1. Third Aspect First, the electron beam recording resist material according to the third aspect of the present invention will be described. The electron beam recording resist material of this aspect is an electron beam recording resist material having a metal compound, wherein the metal element constituting the metal compound is a Group 14 or Group 15 metal element. It is what.

  According to this aspect, by using a metal compound containing a Group 14 or Group 15 metal element, an electron beam recording resist material capable of forming a clear and fine pattern with less exposure can be obtained. . This is due to the fact that the decomposition temperature of the metal compound containing a Group 14 or Group 15 metal element is lower than the decomposition temperature of the metal compound containing a transition metal element used in conventional resist materials. It is. Note that the decomposition temperature of the metal compound is a temperature at which the bond of the metal compound is released only by thermal energy when the temperature exceeds that temperature, and almost coincides with the melting point in most metal compounds, but in a compound having a lower sublimation temperature. Match the sublimation point. That is, in the resist material using the conventional transition metal element, since the decomposition temperature of the transition metal element is high, the sensitivity to the electron beam is low, and many exposures are necessary to obtain a desired pattern. On the other hand, since the electron beam recording resist material of this embodiment has a low decomposition temperature, it has high sensitivity to an electron beam and can form a clear pattern with less exposure.

  The metal compound used in this embodiment may be a “stoichiometrically complete metal compound” or a “stoichiometrically incomplete metal compound”. Since these definitions are the same as the contents described in “A. Resist material” above, description thereof is omitted here. Moreover, the resist material of this aspect may contain the heat generating agent which converts an electron beam into heat. Further, the specific metal compound, the heat generating agent, the method for producing the electron beam recording resist material, and the like are the same as those described in the above “A. Resist material 1. First aspect”. Is omitted. In particular, in this embodiment, the metal compound is preferably a metal oxide.

2. Fourth Aspect Next, the electron beam recording resist material according to the fourth aspect of the present invention will be described. The resist material for electron beam recording according to this aspect is a resist material for electron beam recording having a metal compound, wherein the metal compound is a metal nitride.

  According to this aspect, by using a metal nitride, an electron beam recording resist material capable of forming a clear pattern with less exposure can be obtained. This is because the decomposition temperature of the metal nitride is lower than the decomposition temperature of the metal oxide or the like used in the conventional resist material.

  The metal nitride used in this embodiment may be a “stoichiometrically complete metal compound” or a “stoichiometrically incomplete metal compound”. Since these definitions are the same as the contents described in “A. Resist material” above, description thereof is omitted here. Moreover, the resist material of this aspect may contain the heat generating agent which converts an electron beam into heat. Further, the specific metal nitride, the heat generating agent, the method for producing the electron beam recording resist material, and the like are the same as those described in the above “A. Resist material 2. Second aspect”. Description is omitted.

D. Next, the resist substrate for electron beam recording of the present invention will be described. It has a substrate and an electron beam recording resist film formed on the substrate and using the electron beam recording resist material described above.

  According to the present invention, since the electron beam recording resist film using the above-described electron beam recording resist material is provided, there is an advantage that a clear and fine pattern can be formed with less exposure.

  As the substrate used in the present invention, the same substrate as that used for a general resist substrate can be used. Further, the electron beam recording resist material used in the present invention is the same as that described in “C. Electron beam recording resist material”, and therefore the description thereof is omitted here. Examples of a method for forming an electron beam recording resist film on a substrate include a reactive sputtering method and a vapor deposition method.

  In the present invention, the substrate is preferably a metal substrate, and a heat storage layer is preferably formed between the metal substrate and the resist film. This is because the provision of the heat storage layer has an advantage that heat is maintained in heat mode recording even when a metal substrate having high thermal conductivity is used. The metal substrate, the heat storage layer, and the like are the same as the contents described in “B. Resist substrate”, and thus the description thereof is omitted here.

  In the present invention, an electron beam moderation layer is preferably formed on the electron beam recording resist film. The electron beam decelerating layer is a layer provided to prevent most of the electron beams that enter at a high speed under acceleration voltage from penetrating to the substrate side without reacting with the resist film for electron beam recording. However, when passing through the electron beam moderating layer material, the electron beam is decelerated by collision or the like, so that many electrons react with the resist film, and the electron beam can be efficiently converted into heat.

  FIG. 4 is a schematic cross-sectional view showing an example of an electron beam recording resist substrate having an electron beam deceleration layer. The electron beam recording resist substrate shown in FIG. 4 includes a substrate 1, an electron beam recording resist film 6 formed on the substrate 1, and an electron beam deceleration layer 7 formed on the electron beam recording resist film 6. And.

  As a material for the electron beam moderation layer, a layer whose main component is a resin is suitable. For example, an ultraviolet curable resin, a thermosetting resin, an ultraviolet curable resin used in combination with thermosetting, a solvent volatile curable resin, etc. The thing etc. which contain can be mentioned. Specific examples of such resins include urethane acrylate resins, epoxy acrylate resins, polyester resins, epoxy resins, acrylic resins, urethane resins, styrene resins, melamine resins, polycarbonate resins, polypropylene resins, polyethylene resins, polylactic acid resins, and These mixed resins are mentioned. In addition, a resin used as an electron beam resist (manufactured by Zeon Corporation, ZEP520A, etc.) or the like can be used as an electron beam deceleration layer.

For example, the resin may contain a heat generating agent that absorbs and generates heat with an electron beam. Such a heat generating agent is not particularly limited. For example, noble metals such as Pd, Ag, Au, and Pt, halogen elements such as F, Cl, Br, and I having high electron affinity, LiF, NaCl, and KBr. And metal halides such as CaF ₂ , MgF ₂ , AlF ₃ , and BiF ₃ .

  The thickness of the electron beam decelerating layer is not particularly limited. For example, it is preferably in the range of 10 nm to 600 μm, and more preferably in the range of 50 nm to 100 μm. This is because if the thickness of the electron beam decelerating layer is too thin, the decelerating effect is insufficient, and if it is too thick, the productivity is lowered.

  The method for forming the electron beam decelerating layer is not particularly limited as long as it can obtain the above-described electron beam decelerating layer, and a general coating method can be used.

The electron beam decelerating layer can be easily removed by recording on an electron beam recording resist substrate and then dissolving it using formalin or exposing it to O ₂ plasma.

  Moreover, the resist substrate for electron beam recording of this invention may be equipped with both the thermal storage layer and the electron beam deceleration layer. Specifically, as shown in FIG. 5, a metal substrate 1 ′, a heat storage layer 5 formed on the metal substrate 1 ′, an electron beam recording resist film 6 formed on the heat storage layer 5, and an electron Examples include those having an electron beam decelerating layer 7 formed on the resist film 6 for line recording. When the electron beam recording resist substrate includes a heat storage layer, a metal substrate is usually used as the substrate.

E. Next, the manufacturing method of the pattern formation body of this invention is demonstrated. The pattern forming body manufacturing method of the present invention comprises forming a resist film using the above-described resist material or an electron beam recording resist film using the above-described electron beam recording resist material on a substrate, The resist film or the electron beam recording resist film is irradiated with an electron beam.

  The manufacturing method of the pattern formation body of this invention can be divided roughly into the following two aspects. That is, an embodiment (fifth embodiment) in which an electron beam recording resist film described in "C. Electron beam recording resist material" is used to form an electron beam recording resist film and electron beam irradiation is performed; This is an embodiment (sixth embodiment) in which a resist film is formed using the resist material described in “A. Resist material” and electron beam irradiation is performed. Hereinafter, the two aspects will be described in detail.

1. Fifth Aspect A fifth aspect of the method for producing a pattern forming body of the present invention will be described. In the method for producing a pattern forming body according to this aspect, after forming an electron beam recording resist film using the above-described electron beam recording resist material on a substrate, the electron beam recording resist film is irradiated with an electron beam. It is characterized by doing.

  According to this aspect, the electron beam recording resist film made of the above-described electron beam recording resist material is irradiated with an electron beam that can be irradiated with a spot diameter smaller than that of light irradiation, thereby further reducing the fineness. A pattern forming body having a pattern can be obtained. Although it does not specifically limit as a use of the pattern formation body obtained by this aspect, For example, it can use for an optical device, a magnetic device, a semiconductor device, a display device, etc.

  Hereinafter, with respect to the pattern forming body manufacturing method of this aspect, an electron beam recording resist film forming step of forming an electron beam recording resist film using a resist material for electron beam recording on a substrate, and the above-mentioned electron beam recording Description will be made separately on an exposure process in which a resist film is irradiated with an electron beam to form a latent image pattern, and a development process in which a concave / convex pattern is formed from the latent image pattern.

(1) Electron beam recording resist film forming step This step is a step of forming an electron beam recording resist film made of the above-mentioned electron beam recording resist material on a substrate.
In this step, the method for providing the electron beam recording resist film on the substrate is not particularly limited, and examples thereof include a reactive sputtering method and a vapor deposition method.

  Moreover, the resist film for electron beam recording obtained by this process has a metal compound. Such a metal compound is the same as that described in “C. Resist material for electron beam recording”, and therefore, the description thereof is omitted here. In particular, in this embodiment, the metal element constituting the metal compound is preferably a heavy element. This is because by using a heavy element, the mean free path of electrons at the time of electron collision is shortened, and electrons can react with high density. Therefore, for example, when the metal element constituting the metal compound is a Group 14 or Group 15 metal element, Sn, Sb, Pb, and Bi are preferable.

  Moreover, the resist film for electron beam recording obtained by this process may contain the heat generating agent which converts an electron beam into heat. Such a heat-generating agent is the same as that described in “A. Resist material”, and the description thereof is omitted here.

  Further, the film thickness of the electron beam recording resist film obtained in this step varies depending on the use of the pattern forming body, but may be, for example, in the range of 5 nm to 500 nm, particularly in the range of 10 nm to 100 nm. preferable.

  As a board | substrate used for this process, although it changes with uses of the pattern formation body of this aspect, plastics, such as glass and a polycarbonate, a silicon | silicone, an alumina titanium carbide, nickel, carbon etc. can be mentioned, for example. In this step, a heat storage layer may be provided between the substrate and the electron beam recording resist film, or an electron beam deceleration layer may be provided on the electron beam recording resist film. The heat storage layer and the electron beam decelerating layer are the same as those described in “D. Resist substrate for electron beam recording”, and thus the description thereof is omitted here.

(2) Exposure Step This step is a step of forming a latent image pattern by irradiating the electron beam recording resist film with an electron beam. In this step, when the electron beam recording resist film made of the electron beam recording resist material is irradiated with an electron beam, only a portion heated to a temperature equal to or higher than a predetermined threshold causes a state change. Therefore, a fine pattern smaller than the spot diameter of the electron beam can be formed.

  In this step, the method of irradiating the electron beam recording resist film with an electron beam is not particularly limited, and an apparatus used for general electron beam drawing or the like can be used.

  Further, the acceleration voltage in electron beam irradiation varies depending on the use of the pattern forming body, but is preferably in the range of 5 kV to 500 kV, for example, preferably in the range of 10 kV to 200 kV.

(3) Development process This process is a process of forming a concavo-convex pattern from the latent image pattern. In this step, as described in “A. Resist material” above, the crystal structure of the portion (latent image pattern) heated to a temperature equal to or higher than a predetermined threshold is different from the crystal structure of the other portions. The solubility in the developer changes. Therefore, a concavo-convex pattern corresponding to the latent image pattern can be formed.

  In this step, the method for forming the concavo-convex pattern from the pattern latent image is not particularly limited. For example, wet etching development using an alkali developer or an acid developer, a gas such as argon or fluorocarbon is used. And dry etching development performed in plasma.

  The alkali developer is not particularly limited as long as a desired uneven pattern can be formed. Specifically, tetramethylammonium aqueous solution, potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, Examples thereof include an aqueous sodium carbonate solution. The concentration of the alkali developer is preferably selected appropriately according to the type of metal compound constituting the electron beam recording resist film.

  The acid developer is not particularly limited as long as it can form a desired concavo-convex pattern. Specific examples include an aqueous hydrochloric acid solution, an aqueous acetic acid solution, an aqueous sulfuric acid solution, and an aqueous phosphoric acid solution. Can be mentioned. The concentration of the acid developer is preferably selected as appropriate according to the type of metal compound constituting the electron beam recording resist film.

  In this step, an ultrasonic oscillator may be used during development. As described in the above “A. Resist material”, a portion (latent image pattern) heated to a temperature equal to or higher than a predetermined threshold is considered to form a porous structure. Therefore, the mechanical strength is lower than that of the portion where the porous structure is not formed, and an uneven pattern can be easily obtained by using an ultrasonic oscillator.

The dry etching is not particularly limited as long as it is a gas and an apparatus capable of forming a desired concavo-convex pattern. Specifically, an inert gas such as Ar or CF ₄ is used as an etching gas. Fluorocarbon gas such as C ₂ F ₆ , Fluoromethane gas such as CHF ₃ , Chlorine gas such as Cl ₂ and BCl _3, etc., and dry etching equipment such as ion milling equipment, capacitive coupling type and inductive coupling Type reactive ion etching apparatus. Moreover, it is preferable to appropriately select conditions such as the type, pressure, flow rate, etching apparatus, etching power, and the like of the gas according to the type of metal compound constituting the electron beam recording resist film.

2. Sixth Aspect A sixth aspect of the method for producing a pattern forming body of the present invention will be described. The pattern forming body manufacturing method of this aspect is characterized in that a resist film made of the above-described resist material is formed on a substrate, and then the resist film is irradiated with an electron beam.

  According to this aspect, the resist film made of a resist material containing a stoichiometrically incomplete metal compound is further irradiated with an electron beam that can be irradiated with a smaller spot diameter as compared with light irradiation. A pattern formed body having a fine pattern can be obtained. Although it does not specifically limit as a use of the pattern formation body obtained by this aspect, For example, it can use for an optical device, a magnetic device, a semiconductor device, a display device, etc.

  Hereinafter, with respect to the method for producing the pattern forming body of this aspect, a resist film forming step of forming a resist film using the resist material on the substrate, and electron beam irradiation to the resist film to form a latent image pattern The description will be divided into an exposure process and a development process for forming an uneven pattern from the latent image pattern.

(1) Resist film forming step This step is a step of forming a resist film made of the resist material on the substrate.
In this step, a method for providing a resist film on the substrate is not particularly limited, and examples thereof include a reactive sputtering method and a vapor deposition method. Since such a method is the same as the method described in “A. Resist material”, description thereof is omitted here.

  Further, the resist film obtained by this step has a stoichiometrically incomplete metal compound. Such a metal compound is the same as that described in the above “A. Resist material”, and the description thereof is omitted here. In particular, in this embodiment, the metal element constituting the metal compound is preferably a heavy element. This is because by using a heavy element, the mean free path of electrons at the time of electron collision is shortened, and electrons can react with high density. Therefore, for example, when the metal element constituting the metal compound is a Group 14 or Group 15 metal element, Sn, Sb, Pb, and Bi are preferable.

  Other matters such as the film thickness of the resist film and the type of the substrate are the same as the contents described in the above-mentioned “E. Manufacturing method of pattern forming body 1. Fifth aspect”, and thus the description thereof is omitted. .

(2) Other Steps The exposure step and the development step in this embodiment are the same as those described in the above-mentioned “E. Method for producing pattern-formed body 1. Fifth embodiment”, and thus the description thereof is omitted here. To do.

F. Others As described above, the present invention can provide the following inventions.
1. A resist substrate having a substrate and a resist film formed on the substrate and using a resist material,
The resist material has a metal compound, the metal element constituting the metal compound is a Group 14 or Group 15 metal element, the metal compound is a metal oxide, and the metal compound has a stoichiometric amount. The above-mentioned metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, and X is a composition ratio of O in the metal compound). When X is 100%, X in the metal compound is in the range of 75% to 95%,
A resist substrate, wherein the substrate is a metal substrate, and a heat storage layer is formed between the metal substrate and the resist film.
2. A resist substrate having a substrate and a resist film formed on the substrate and using a resist material,
The resist material has a metal compound, the metal element constituting the metal compound is a Group 14 or Group 15 metal element, the metal compound is a metal oxide, and the metal compound has a stoichiometric amount. The above-mentioned metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, and X is a composition ratio of O in the metal compound). When X is 100%, X in the metal compound is in the range of 75% to 95%,
A resist substrate, wherein an electron beam moderation layer is formed on the resist film.
3. The metal element having a metal compound and constituting the metal compound is a Group 14 or Group 15 metal element, the metal compound is a metal oxide, and the metal compound is stoichiometrically incomplete. The above metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, X is a composition ratio of O in the metal compound), and X which is a stoichiometric composition ratio is 100% In this case, after forming a resist film on the substrate using a resist material in which X in the metal compound is in the range of 75% to 95%, the resist film is irradiated with an electron beam. A method for producing a featured pattern formed body.
4). A resist substrate having a substrate and a resist film formed on the substrate and using a resist material,
The resist material has a metal compound, the metal compound is a metal nitride, and the metal compound is a stoichiometrically incomplete compound,
A resist substrate, wherein the substrate is a metal substrate, and a heat storage layer is formed between the metal substrate and the resist film.
5. A resist substrate having a substrate and a resist film formed on the substrate and using a resist material,
The resist material has a metal compound, the metal compound is a metal nitride, and the metal compound is a stoichiometrically incomplete compound,
A resist substrate, wherein an electron beam moderation layer is formed on the resist film.
6). After forming a resist film using a resist material having a metal compound, the metal compound is a metal nitride, and the metal compound is a stoichiometrically incomplete compound on the substrate, A method for producing a pattern forming body, wherein the resist film is irradiated with an electron beam.
7). A resist material having a metal compound, wherein the metal element constituting the metal compound is Bi, and the metal compound is a stoichiometrically incomplete compound.
8). 8. The resist material as described in 7 above, wherein the metal compound is a metal oxide.
9. 8. The resist material as described in 7 above, wherein the metal compound is a metal nitride.
10. A resist material having a metal compound, wherein the metal compound is a metal oxide, the metal compound is a stoichiometrically incomplete compound, and the metal elements constituting the metal compound are Bi, Sn, and A resist comprising at least one metal element selected from the group consisting of Ge and at least one metal element selected from the group consisting of Si, Cu, Fe, Ti and Al material.
11. A resist material having a metal compound, wherein the metal compound is a metal nitride, the metal compound is a stoichiometrically incomplete compound, and a metal element constituting the metal compound is formed from Bi and Sn. A resist having at least one metal element selected from the group consisting of, and at least one metal element selected from the group consisting of Ge, Si, Cu, Fe, Ti, and Al. material.
12 When the metal compound is M _1-X A _X (M is a metal element, A is a non-metal element, X is a composition ratio of A in the metal compound), and X which is a stoichiometric composition ratio is 100% 12. The resist material as described in any one of 7 to 11 above, wherein X in the metal compound is in the range of 75% to 95%.
13. A resist material for electron beam recording comprising a metal compound, wherein the metal element constituting the metal compound is Bi.
14 14. The resist material for electron beam recording as described in 13 above, wherein the metal compound is a metal oxide.
15. 14. The resist material for electron beam recording as described in 13 above, wherein the metal compound is a metal nitride.
16. An electron beam recording resist material having a metal compound, wherein the metal compound is a metal oxide, and the metal element constituting the metal compound is at least one selected from the group consisting of Bi, Sn, and Ge And a resist material for electron beam recording, comprising: at least one metal element selected from the group consisting of Si, Cu, Fe, Ti, and Al.
17. An electron beam recording resist material having a metal compound, wherein the metal compound is a metal nitride, and the metal element constituting the metal compound is at least one selected from the group consisting of Bi and Sn A resist material for electron beam recording, comprising: an element; and at least one metal element selected from the group consisting of Ge, Si, Cu, Fe, Ti, and Al.
18. The metal compound is a metal nitride, and the metal compound is M _1-X A _X (M is a metal element, A is a nonmetal element, and X is a composition ratio of A in the metal compound), and a stoichiometric composition ratio. 18. The resist for electron beam recording according to any one of 13 to 17 above, wherein X in the metal compound is in the range of 75% to 95% when X is 100% material.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

[Example 1]
Using a polycarbonate resin substrate having a thickness of 1.1 mm and a diameter of 12 cm, a Bi—Ge—N resist film having a thickness of 60 nm is formed on the substrate, and a Bi—Ge target is used with an Ar gas of 70 sccm and an N ₂ gas of 20 sccm. In this atmosphere, a nitrogen-introduced film was formed by reactive sputtering. As a result of analyzing the resist film with an X-ray electron spectrometer: X-ray Photoelectron Spectroscopy (XPS), the atomic ratios were Bi: 10 atomic%, Bi-N: 62 atomic%, and Ge-N: 28 atomic%.

  Next, a 1-7 modulation random pattern was recorded from the resist film side using an optical head with a linear velocity of 4.92 m / s, a wavelength of 405 nm, and an objective lens numerical aperture of 0.85. The recording laser power was 8 mW, multipulse was used for recording, and the window width was 15.15 nsec.

  Next, wet etching development was performed in a tetramethylammonium hydroxide solution (2.38% aqueous solution) of an alkali developer. Since Bi—Ge—N hardly dissolves in the tetramethylammonium hydroxide solution, etching was performed for 19 minutes by applying ultrasonic waves while being immersed in a developer so that the etching was accelerated and the etching was uniformly performed on the entire surface. After etching, the sample was sufficiently washed with pure water and dried by air blow to obtain a sample. As a result, as shown in FIG. 6, the mark portion was selectively etched, and it was confirmed that it functions as a resist.

[Example 2]
Instead of the alkali development in Example 1, acid development was performed. Since Bi—Ge—N is dissolved in an acid, wet etching development was performed using a 0.05% acetic acid aqueous solution as an acid developer. Specifically, etching was performed for 19 minutes by applying ultrasonic waves while being immersed in a developer so that the etching was accelerated and performed uniformly over the entire surface. After etching, the sample was sufficiently washed with pure water and dried by air blow to obtain a sample. As a result, it was confirmed that the mark portion was selectively etched in acid development as shown in FIG. 7 to function as a resist.

  As described above, in the present invention, a clear and fine pattern can be formed with less exposure by using a stoichiometrically incomplete metal compound like the Bi-Ge-N resist film. Resist material.

[Example 3]
Using a silicon substrate having a thickness of 0.38 mm and a diameter of 3 inches, a ZnS—SiO ₂ film having a thickness of 20 nm was formed as a heat storage layer on the substrate by a sputtering method, and then Bi having a thickness of 400 nm was formed thereon. the -ge-N resist film was nitrogen introduction deposited by reactive sputtering Bi-Ge target in an atmosphere of _{N 2} gas 20sccm against Ar gas 70 sccm.

  Next, a line pattern having a linear velocity of 0.2 m / s and a pitch width of 0.32 μm was recorded from the resist film side using an electron beam having an acceleration voltage of 50 keV, a beam current of 900 nA, and a beam diameter of about 100 nm.

  Next, wet etching development was performed in a 0.02% acetic acid aqueous solution of an acid developer. Specifically, etching was performed for 19 minutes by applying ultrasonic waves while being immersed in a developer so that the etching was accelerated and performed uniformly over the entire surface. After etching, the sample was sufficiently washed with pure water and dried by air blow to obtain a sample. As a result, as shown in FIG. 8, it was confirmed that the recording line portion was selectively etched to function as a resist.

[Example 4]
Using a silicon substrate having a thickness of 0.38 mm and a diameter of 3 inches, a ZnS—SiO ₂ film having a thickness of 400 nm was formed on the substrate as a heat storage layer by a sputtering method, and then Bi having a thickness of 200 nm was formed thereon. A -O resist film was formed by introducing oxygen into the Bi target by reactive sputtering in an atmosphere of 10 sccm of O ₂ gas with respect to 80 sccm of Ar gas.

  Next, a line pattern having a linear velocity of 0.2 m / s and a pitch width of 0.32 μm was recorded from the resist film side using an electron beam having an acceleration voltage of 50 keV, a beam current of 900 nA, and a beam diameter of about 100 nm.

  Next, wet etching development was performed in a 10% nitric acid aqueous solution of an acid developer. Specifically, it was immersed in a developing solution and etched for 45 seconds. After etching, the sample was sufficiently washed with pure water and dried by air blow to obtain a sample. As a result, as shown in FIG. 9, although the exposure time and development time are slightly too long and a part of the line pattern has collapsed, the recording line portion is selectively etched, and in principle It was confirmed that it functions as a resist.

[Example 5]
With respect to the resist substrate similar to that of Example 4, from the resist film side, using an electron beam with an acceleration voltage of 50 keV, a beam current of 900 nA, and a beam diameter of about 100 nm, a linear velocity of 1.0 m / s and a pitch width of 0 A line pattern of 32 μm was recorded.

Next, instead of the acid development in Example 4, dry etching development was performed. Specifically, using a reactive ion etching apparatus, CHF ₃ gas is supplied as an introduction gas at a pressure of 0.5 Pa and a flow rate of 50 sccm, and the plasma generation antenna RF power is 50 W, the substrate bias RF power is 10 W, and the substrate temperature is 20 ° C. Then, etching was performed for 10 minutes to obtain a sample. As a result, in the dry etching development, it was confirmed that the recording line portion was selectively etched as shown in FIG. 10 to function as a resist.

It is explanatory drawing which shows a state change when light is exposed to the resist material of this invention. It is explanatory drawing which shows a state change when light is exposed to the resist material of this invention. It is a schematic sectional drawing which shows an example of the resist board | substrate of this invention. It is a schematic sectional drawing which shows an example of the resist substrate for electron beam recording of this invention. It is a schematic sectional drawing which shows the other example of the resist substrate for electron beam recording of this invention. 3 is an image showing the result of alkali development in Example 1. 6 is an image showing the result of acid development in Example 2. 6 is an image showing the result of acid development in Example 3. 6 is an image showing the result of acid development in Example 4. 10 is an image showing the result of dry etching development in Example 5.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate 1 '... Metal substrate 2 ... Resist film 3 ... Recording part 4 ... Unrecorded part 5 ... Thermal storage layer 6 ... Resist film for electron beam recording 7 ... Electron beam deceleration layer

Claims (2)

A resist substrate having a substrate and a resist film formed on the substrate and using a resist material,
The resist material has a metal compound, the metal element constituting the metal compound is Bi, the metal compound is a metal oxide, and the metal compound is a stoichiometrically incomplete compound, When the metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, X is a composition ratio of O in the metal compound), and X which is a stoichiometric composition ratio is 100%, X in the metal compound is in the range of 75% to 95%,
An electron beam moderation layer is formed on the resist film. A metal element comprising the metal compound, the metal element constituting the metal compound is Bi, the metal compound is a metal oxide, the metal compound is a stoichiometrically incomplete compound, and the metal compound is M _1-X O _X (M is a metal element, O is an oxygen element, X is a composition ratio of O in the metal compound), and X is 100% as the stoichiometric composition ratio. A resist film made of a resist material with X in the range of 75% to 95% is formed on a substrate, an electron beam moderation layer is formed on the resist film, and then the resist film is irradiated with an electron beam. A method for producing a pattern forming body, which is performed.