JP4411033B2 - Structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to a structure and a method for producing the same, and a mixture of aluminum and silicon, particularly a mixture containing boron, nitrogen, hydrogen, and carbon, a porous body obtained from the mixture, and a method for producing the same. In particular, fine pores having an average pore diameter of 10 nm or less and an average interval of 15 nm or less are separated from each other by a silicon region, and the pores are formed perpendicular or almost perpendicular to the membrane surface. The present invention relates to a structure and a manufacturing method thereof.

  Metal and semiconductor thin films, thin wires, dots, and the like may exhibit unique electrical, optical, and chemical properties by confining the movement of electrons in a size smaller than a certain characteristic length. From such a viewpoint, as a functional material, there is an increasing interest in a material (hereinafter, “nano mixture”) having a structure having a size (width, thickness, etc.) finer than several tens of nm. As a method for producing such a nanomixture, for example, a method of directly producing a nanomixture by a semiconductor processing technique including a fine pattern forming technique such as photolithography, electron beam exposure, and X-ray exposure is cited. It is done.

  However, direct nanomixture production by this semiconductor processing technique has problems such as poor yield and high device cost, and a technique that can be produced with a simple technique and good reproducibility is desired.

  Therefore, in addition to the method for producing nanomixtures by semiconductor processing technology, let us realize a novel nanomixture based on a naturally formed regular structure, that is, a self-regularly formed structure. There is an attempt to do. Many of these techniques are being studied because there is a possibility that a fine and special structure can be produced over the conventional method depending on the fine structure used as a base.

  As such a self-regular method, anodization capable of forming a nano mixture having nano-sized pores in a large area with good control can be mentioned. For example, anodized alumina prepared by anodizing aluminum in an acidic bath is known.

  First, in anodization of aluminum, when an aluminum film formed on an aluminum plate or substrate is anodized in an acidic electrolyte, a porous oxide film (anodized alumina) is formed. The feature of this porous oxide film is the uniqueness that extremely fine cylindrical pores (nanoholes) with a diameter of several nanometers to several hundred nanometers are arranged in parallel at intervals (cell size) of several tens of nanometers to several hundred nanometers It has a typical geometric structure. These cylindrical pores have a high aspect ratio and relatively excellent cross-sectional diameter uniformity when the pore spacing is several tens of nanometers or more. The diameter and interval of the pores can be controlled to some extent by adjusting the type of acid and voltage in anodization. Specifically, when the voltage is lowered, the interval between the pores can be reduced. Further, the thickness of the anodized film and the depth of the pores can be controlled to some extent by controlling the anodizing time.

  In addition, various applications have been attempted focusing on the specific geometric structure, color, and durability of the anodized alumina. Detailed explanation by Non-Patent Literature 2 is detailed, but application examples are listed below. For example, there is an application to a filter by peeling a film. Furthermore, by using technology to fill metals, semiconductors, etc. in nanoholes and replica technology of nanoholes, including coloring, magnetic recording media, EL light emitting devices, electrochromic devices, optical devices, solar cells, gas sensors, etc. Various applications have been attempted. Furthermore, it is expected to be applied to various fields such as quantum effect devices such as quantum wires and MIM elements, and molecular sensors using nanoholes as chemical reaction fields (see Non-Patent Document 1).

  In addition to such anodized alumina, as a method for producing a nanomixture having nanosized pores, there is anodization of silicon. In the anodization of silicon, porous silicon is formed when anodization of crystalline silicon or polycrystalline silicon in an aqueous solution based on HF (hydrofluoric acid) is performed (see Non-Patent Document 2, etc.). This porous silicon has innumerable micropores of about 1 to several tens of nm on the surface or inside. The macropores have a structure substantially perpendicular to the film surface when viewed macroscopically, but their shape and density vary greatly depending on the conditions of anodization.

From this point of view, the self-regular method, particularly the method of anodizing aluminum or anodizing silicon, is notable for its ability to easily produce a nanomixture in a large area. In particular, the structure in which micropores in anodized alumina or anodized silicon (porous silicon) are made perpendicular to the substrate and at a very high density can be applied to devices using quantum effects, or This is important for producing a high-density recording medium.
Masuda, "Solid Physics" 31, 1996, p.493 DR Turner: "J. Electrochem. Soc." 105, 1985, p.402 MIJ Beale, NG Chew, MJ Uren, AG Cullis, JD Benjamin: Appl.Phys. Lett. 46, 1985, p.86

  On the other hand, the present inventors can form nanoholes with an average pore diameter of 10 nm or less as a nanomixture in a high density in the process of studying the application form of such nanomixtures to devices. If it exists, it came to the recognition that the application range to the device of a nano mixture could be expanded further. That is, for example, by forming nanoholes having a pore diameter of 10 nm or less at intervals of 15 nm or less and forming an electrically conductive material such as metal or semiconductor in the nanoholes, it can be applied to quantum effect devices such as single-electron memories and single-electron transistors.

  In addition, if the material constituting the nanomixture is a material mainly composed of silicon, the resistance to acids and alkalis is higher than that of aluminum oxide produced by anodization, and the nanomixture can be applied to devices. We came to realize that the range of applications could be expanded.

  However, in the anodization of aluminum, when the anodic oxidation voltage is lowered in order to make the pore interval 10 nm or less, the mutual pores 81 and 82 are formed of anodized alumina 83 as shown in FIG. It becomes difficult to make the pores independent by separating the walls. Further, since the base material is alumina made by anodic oxidation, it dissolves relatively easily in acids and alkalis and is inferior in durability to chemicals. Further, as shown in FIG. 8, an anodized alumina film called a barrier layer 85 is formed between the substrate 84 and the pores 81 and 82 at the lower part of the pores. When filling with plating, a process of removing the barrier layer, a method using an alternating electric field, and the like are required.

  Further, in the anodization of silicon, when viewed macroscopically, the pores are formed perpendicular to the film surface. However, when observed in more detail, the pores 91 are randomly or dendriticly as shown in FIG. Therefore, the shape of the pores is not constant, and it may be difficult to adapt to quantum effect devices such as single-electron memory and single-electron transistor. (Refer nonpatent literature 3).

  Due to such technical background, the present inventors have conducted various studies. As a result, the average pore diameter of the pores is 10 nm or less, and the average interval between the pores is 15 nm or less, and the pores are columnar. Independently from each other and perpendicular or nearly perpendicular to the membrane surface, the wall material separating the pores is made of silicon highly resistant to chemicals, and the substrate and the pores can be directly connected The present inventors have found a method capable of forming a silicon nanomixture and have reached the present invention.

  That is, the present invention provides a silicon nanomixture having a novel configuration that can further expand the range of application to various devices.

  Moreover, this invention provides the manufacturing method of the silicon nano mixture which has a novel structure which can expand the application range to the device which has a novel structure more.

  The structure according to the present invention is a structure composed of a columnar first member and a second member surrounding the first member. The structure includes at least one of boron, nitrogen, hydrogen, and carbon. It is characterized by containing the following components.

  The first member preferably contains aluminum.

  The second member preferably contains silicon or silicon and germanium.

  The proportion of at least one component of boron, nitrogen, hydrogen, and carbon is preferably 30 atomic% or less with respect to the total of the first member and the second member. More preferably, it is 0.5 atomic% or more and 20 atomic% or less.

  The first member preferably has a diameter of 50 nm or less. More preferably, it is 10 nm or less.

  The first member has an interval of 30 nm or less, more preferably 15 nm or less.

  It is also preferable to constitute a structure having holes formed by removing the first member from the structure.

  The manufacturing method of the structure according to the present invention is mainly composed of aluminum and silicon germanium (including the case of only silicon but excluding the case of only germanium) on the substrate, and contains boron, nitrogen, hydrogen, and carbon. A film including at least one element is formed by a non-equilibrium film forming method to form a columnar first member composed mainly of aluminum and silicon surrounding the first member. And a second member having a germanium region, and a structure containing at least one element of boron, nitrogen, hydrogen, and carbon at a ratio of 30 atomic% or less.

  The structure manufacturing method according to the present invention is a film in which a film mainly composed of aluminum and silicon germanium (including the case of only silicon and excluding only germanium) is formed on a substrate in a non-equilibrium state. Forming a structure having a columnar first member comprising aluminum and a second member having a silicon germanium region surrounding the first member, and the structure And adding at least one element of boron, nitrogen, hydrogen, and carbon at a ratio of 30 atomic% or less with respect to the total of aluminum and silicon germanium.

  The structure manufacturing method may further include a step of selectively removing only the columnar first member including aluminum and forming columnar pores.

The present invention is a structure composed of a mixture formed of a first material and a second material, or a porous body from which the first material is removed, and boron, nitrogen, or hydrogen In addition, by containing carbon, the formation of the two kinds of structures can be prevented, and acid resistance, alkalinity improvement, and wear resistance improvement can be achieved. Thereby, the silicon nanomixture which has a novel structure which can expand the application range to various devices more, and its manufacturing method can be provided.

  Embodiments of a structure and a method for manufacturing the structure according to the present invention will be described below with reference to FIGS.

  In the present embodiment, the first material and the second material are characterized by containing at least one of boron, nitrogen, hydrogen, and carbon as the third material. As a method shown, when the first material is A, the second material is B, and the third material is C, the composition of the material is expressed using x and y included in the following formula. .

(A _x B _1-x ) _y C _1-y
Here, x and y can take values between 0 and 1, and can be converted to atomic% by multiplying by 100. Hereinafter, this notation is applied to the composition of the material.

(Embodiment 1: Mixture)
This embodiment is applied to a mixture. The mixture according to this embodiment will be described with reference to FIG.

  FIG. 1 shows a region (first member) 11 having a columnar structure and having a first material as a main component, and a region (second member) 12 having a second material as a main component that surrounds it. FIG. 1A and FIG. 1B are a top view and a cross-sectional view, respectively. Reference numeral 13 denotes a substrate.

  In the mixture 14 in FIG. 1, a region 11 containing a first material as a main component is surrounded by a region 12 containing a second material as a main component, and the mixture 14 contains a second material. , 0.3 ≦ x ≦ 0.8 (20 atomic% or more and 70 atomic% or less). When the ratio is within this range, it is possible to provide the mixture 14 in which substantially columnar members are dispersed in a matrix region surrounding the member.

  Although depending on the shape of the underlying substrate on which the mixture 14 is formed, if the substrate shape is horizontal, the columnar members are arranged substantially perpendicular to the substrate 13. In this case, one or more elements of boron, nitrogen, hydrogen, or carbon contained in the mixture 14 may be dispersed in both the first material and the second material. However, boron, nitrogen, hydrogen, or carbon must be contained in a ratio of 0.7 ≦ y <1 (30 atomic% or less) with respect to the total of the first material and the second material. Is preferred. Further, preferably 0.8 ≦ y ≦ 0.995 (0.5 atomic% or more and 20 atomic% or less). However, since it is difficult to quantitatively determine boron, nitrogen, hydrogen, or carbon within this ratio range, it does not exclude that some fluctuation occurs in the ratio.

  The ratio of the second material is preferably a ratio that satisfies 0.35 ≦ x ≦ 0.75, and more preferably a ratio that satisfies 0.40 ≦ x ≦ 0.70. This ratio can be obtained, for example, by quantitative analysis by inductively coupled plasma emission spectrometry.

  In particular, when the second material is silicon or silicon germanium and boron, nitrogen, or hydrogen is used to control the conductivity type of the material, boron, nitrogen, or hydrogen is added to the first material and the second material. For the purpose of giving sufficient controllability to an amount satisfying y ≧ 0.995 (0.5 atomic% or less) with respect to the total of the materials, and y ≦ 0.995 (0. 5 atomic% or more) is preferable.

  The mixture 14 only needs to have a substantially columnar shape. For example, the mixture 14 may contain a second material as a component of the columnar member, or the second material as a main component. The region 12 may contain a first material. Further, the region 11 forming the columnar member and the surrounding region 12 may contain impurities such as oxygen and argon.

Examples of the first material include Al and Au. _{Examples of} the second material include Si, Ge, a mixture of Si and Ge (hereinafter, sometimes referred to as SizGe1 _-z (0 <z <1)), or C. In particular, the second material is preferably a material that can be amorphous. The first and second materials are preferably materials having eutectic points (so-called eutectic materials) in the component phase equilibrium diagram of both. In particular, the eutectic temperature is 300 ° C or higher, preferably 400 ° C or higher. A eutectoid material can also be used.

A preferred combination of the first material and the second material is a form using Al as the first material and Si as the second material, or using Al as the first material and Si _z as the second material. A form using Ge _1-z (0 <z <1) can be mentioned.

  The region 11 forming the columnar member is preferably at least partially polycrystalline, and the region 12 surrounding the columnar member is preferably amorphous. The planar shape of the columnar member formed of the region 11 is circular or elliptical. Further, it is also preferable that a part of the amorphous portion is microcrystalline in the region 12 surrounding the columnar member by containing boron, nitrogen, hydrogen, or carbon. In other words, the presence of the microcrystal is important because it is reflected in the electrical characteristics of the electronic device, the medium strength of the magnetic recording medium, and the like.

  In the mixture 14, a plurality of columnar members, that is, the region 11 mainly composed of the first material is dispersed in the region 12 mainly composed of the second material. The diameter of the columnar member formed of the region 11 (the diameter when the planar shape is a circle) can be controlled mainly depending on the composition of the mixture 14 (that is, the ratio of the second material), etc. Is 0.5 nm to 50 nm, preferably 1 nm to 20 nm, and more preferably 2 nm to 10 nm. Particularly, the diameter is preferably less than 20 nm.

  The “diameter” here is 2r in FIG. In the case of an ellipse or the like, the longest outer diameter portion may be within the above range. Here, the “average diameter” is, for example, a value derived from a columnar portion observed in an actual SEM photograph (in the range of about 100 nm × 100 nm) directly from the photograph or by image processing with a computer. is there. However, the optimum diameter and the following interval may vary depending on the material and composition used or the application of the mixture 14.

In addition, the center-to-center distance 2R (FIG. 1B) between the plurality of columnar members (regions 11) is 2 nm to 30 nm, preferably 5 nm to 20 nm, and more preferably 5 nm to 15 nm. Of course, as the lower limit of the center-to-center distance, the above-mentioned 2R needs to have a minimum interval at which the columnar structures do not contact each other. Note that a mixture of a plurality of elements (for example, Si _z Ge _1-z (0 <z <1)) is used as the second material (that is, the material surrounding the region 11 containing the first material as a main component). For example, the center-to-center distance between the columnar members can be controlled by the ratio of the mixing ratio. Here, the center-to-center distance between the columnar members (regions 11) is the center-to-center distance between the columnar members (regions 11) adjacent to each other.

  In addition, the mixture 14 is preferably a film-like mixture. In such a case, the region 11 mainly composed of the columnar first material is substantially perpendicular to the in-plane direction of the film. Are dispersed in the region 12 containing the second material as a main component. Although it does not specifically limit as a film thickness of a film-form mixture, It is applicable in the range of 1 nm-100 micrometers. A more realistic film thickness in consideration of process time and the like is about 1 nm to 1 μm, or 1 nm to 3 μm. In particular, the columnar structure is preferably maintained even with a film thickness of 300 nm or more. The columnar member preferably has a structure that does not substantially branch in the thickness direction L (length direction).

  The mixture 14 is preferably a film-like mixture, and the mixture may be provided on a substrate. The substrate 13 is not particularly limited, but in the case of an insulator or a substrate having an insulating layer on its surface, an insulating substrate such as quartz glass, tempered glass, crystallized glass, glass, silicon substrate, gallium arsenide Alternatively, if the above mixture can be formed on a semiconductor substrate such as indium phosphide, a metal substrate such as aluminum, or a substrate as a support member, a flexible substrate (for example, a polyimide resin) can also be used. In the case of a silicon substrate, a p-type, n-type, high-resistance substrate, low-resistance substrate, or the like can be used as appropriate.

  Note that an electronic device can be provided by further forming an insulating film or the like over the mixture 14. Here, the electronic device is a quantum dot, a quantum wire, a quantum wire transistor, a single electron transistor, a single electron memory, or the like, and further includes an information processing device including them.

  The mixture in the present embodiment (hereinafter sometimes referred to as a mixture) can be applied as various base materials, and can be applied to various quantum devices such as single-electron transistors and single-electron memories, microelectrodes, and the like.

  Moreover, the mixture (for example, aluminum silicon mixture) in this embodiment can be used as a mask for dry etching or wet etching for the purpose of processing another substrate or a film on the substrate.

  In addition, the present embodiment makes it possible to apply columnar structures such as quantum dots and quantum wires in various forms, and greatly expands the application range. The mixture in the present invention can itself be used as a functional material.

(Embodiment 2: Method for producing a mixture)
This embodiment is applied to the manufacturing method of the mixture 14 of Embodiment 1 mentioned above. The mixture 14 of the first embodiment can be manufactured using a method of forming a film in a non-equilibrium state. As the film formation method, the sputtering method (physical vapor deposition method) shown in FIG. 2 is preferable. However, the material is applied in any non-equilibrium state including resistance heating vapor deposition, electron beam vapor deposition (EB vapor deposition), and ion plating method. A film forming method to be formed is applicable.

  With reference to FIG. 2, the manufacturing method of the mixture by sputtering method is demonstrated.

  When the sputtering method is used, magnetron sputtering, RF sputtering, ECR sputtering, or DC sputtering can be used. When the sputtering method is used, the film is formed in an argon gas atmosphere at a pressure in the reactor of about 0.2 to 1 Pa, or about 0.1 to 1 Pa. Further, sputtering in a low gas pressure region of 0.1 Pa or less may be used, and other rare gases may be used as gas species, and it is also preferable to partially mix nitrogen, hydrogen, oxygen, or the like.

  In sputtering, the first material and the second material may be separately prepared as target 22 materials (for example, a target 22 material in which aluminum and silicon are separated is used), but a desired material is used in advance. You may use target 22 material by which the 1st material and the 2nd material were baked in the ratio.

  As for boron, nitrogen, and carbon, a compound with the first or second material may be arranged as a chip 23 in a part of the target 22 material, and a target obtained by sintering a raw material containing a desired amount in advance. It is also preferable to prepare 22. In the mixture according to this embodiment, the columnar member and the region surrounding the side surface are formed at the same time. It is also preferable to perform sputtering in a state where Ar plasma is not in contact with the substrate 21 on which the film is grown.

  Moreover, it is also preferable to implant boron and the like by an ion implantation method.

  In addition, the mixture according to the present embodiment can maintain a state in which the side surfaces of the members forming the columnar structure are dispersed in the region surrounding the mixture even when the film thickness is greater than a predetermined thickness. That is, even when the film thickness is increased, the diameter of the columnar structure does not change greatly with respect to the film thickness direction. The predetermined film thickness is 110 nm or more, more preferably 300 nm or more.

  The mixture formed on the substrate can be manufactured at a substrate temperature of 300 ° C. or lower, preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower.

(Embodiment 3: Aluminum silicon mixture)
In the present embodiment, the mixture of Embodiment 1 described above is applied to an aluminum silicon mixture. The mixture in the case where the first and second materials are aluminum and silicon will be described with reference to FIG. 1 described in the first embodiment again.

  This embodiment corresponds to the case where the first material in FIG. 1 is aluminum and the second material is silicon. That is, FIG. 1 (a) is a schematic plan view of an aluminum silicon mixture containing boron, nitrogen, hydrogen, or carbon according to the present invention. FIG. 1B is a schematic cross-sectional view when the sample is cut along the broken line AA ′ in FIG.

  The aluminum-silicon mixture containing film-form boron, nitrogen, hydrogen, or carbon formed on the substrate preferably has a ratio of aluminum to silicon of 0.3 ≦ x ≦ 0.8. Further, preferably 0.35 ≦ x ≦ 0.75, and more preferably 0.4 ≦ x ≦ 0.7. If the ratio of aluminum to silicon is within the above range, an aluminum silicon mixture in which columnar structures are dispersed in the silicon region can be obtained.

  The ratio of aluminum to silicon is a value when the amount of silicon and aluminum in the aluminum silicon mixture film is quantitatively analyzed by, for example, inductively coupled plasma emission spectrometry. Further, the content of boron, nitrogen, hydrogen, or carbon with respect to aluminum and silicon is preferably y ≧ 0.7, more preferably 0.8 ≦ y ≦ 0.995. It is preferable that Further, when boron, nitrogen, or hydrogen is used for controlling the conductivity type of the material, the amount satisfying y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ It is preferable to satisfy 0.995.

  The aluminum silicon mixture containing boron, nitrogen, hydrogen, or carbon in the present embodiment includes an aluminum columnar structure having a composition containing aluminum as a main component, and a silicon region having silicon as a main component around the aluminum columnar structure. Is provided.

  Moreover, the composition of the columnar structure portion containing aluminum is mainly composed of aluminum, but if a fine mixture of columnar structures is obtained, boron, nitrogen, hydrogen, or carbon is included. Is preferred. Furthermore, other elements such as silicon, oxygen, and argon may be contained. Note that the main component means that, for example, the ratio of aluminum in the component composition ratio of the columnar structure portion is 50 atomic% or more, and more preferably 80 atomic% or more.

  The composition of the silicon region surrounding the columnar structure is mainly composed of silicon, but boron, nitrogen, hydrogen, or carbon can be used if a fine mixture having a columnar structure is obtained. It is preferable to include. Furthermore, you may contain various elements, such as aluminum, oxygen, and argon. Note that the main component is, for example, that the proportion of silicon in the component composition ratio of the silicon region is 50 atomic% or more, and more preferably 80 atomic% or more.

  The silicon region is preferably amorphous. In addition, it is preferable that the silicon region portion is amorphous silicon from the viewpoint of insulation. This is because amorphous silicon has a higher defect density and a larger band gap than crystalline silicon, so that the electrical insulation of the base material separating the columnar structures is improved. In addition, it is also preferable that a part of the crystalline portion is present in the amorphous portion microscopically in the silicon region portion by containing boron, nitrogen, hydrogen, or carbon. In other words, the presence of the microcrystal is important because it is reflected in the electrical characteristics in the later electronic device, the medium strength in the magnetic recording medium, and the like.

  The mixture used here indicates a state in which aluminum is liberated in the silicon matrix.

  The columnar structure including aluminum has a circular shape or an elliptical shape as viewed from the film surface. Of course, any shape may be used as long as the columnar structures are appropriately dispersed in the silicon region.

  The diameter of the columnar structure in the aluminum silicon mixture according to the present embodiment is not particularly limited, but the average diameter is 0.5 nm to 50 nm, preferably 0.5 nm to 20 nm, and more preferably 0. It should be 5 nm or more and 10 nm or less. The diameter here is 2r in FIG. In the case of an ellipse or the like, the longest outer diameter portion may be within the above range. Here, the average diameter is a value derived, for example, by image processing of an aluminum portion observed in an actual SEM photograph (a range of about 100 nm × 100 nm) with a computer.

  By the way, nanometer-sized nanomixtures (generally in the range of 0.1 nm to 100 nm) have a size smaller than a certain characteristic length. May show chemical and chemical properties. From such a viewpoint, the nanomixture is useful as a functional material, and also in the aluminum silicon mixture according to the present embodiment, the diameter of the columnar structure constituting the mixture is 0.5 nm to 50 nm, particularly When it is 0.5 nm or more and 10 nm or less, various uses are possible as a nano mixture.

  The center-to-center distance 2R (see FIG. 1B) of the plurality of columnar structures is 30 nm or less, preferably 15 nm or less. Of course, the 2R has an interval at which the columnar structures do not contact each other. In particular, both the diameter 2r and the center-to-center distance 2R are preferably within the above ranges.

  For example, the diameter of the aluminum nanostructure is 1 to 9 nm, the distance between the aluminum nanomixtures is 5 to 10 nm, and the height to diameter ratio of the aluminum nanomixture is 0.1 to 100,000. And a fine mixture in which the aluminum nanomixture is perpendicular to the substrate.

  Further, the shape of the columnar structure viewed from the cross section of the substrate is preferably a rectangular shape as shown in FIG. 1B, but may take a shape such as a square or a trapezoid. The columnar structure includes a shape having an arbitrary aspect ratio (diameter / length). For example, the aspect ratio (diameter 2r / length L) can be 0.1 to 100,000.

  For example, the length L of the columnar structure can be applied in the range of 1 nm to 100 μm.

  In particular, consider a case where the length L is controlled in the range of 1 nm to several μm when the diameter 2r of the columnar structure is, for example, 1 to 10 nm and the center-to-center distance 2R is 5 to 15 nm. When the length L is several nanometers to several tens of nanometers (when the ratio of length to diameter is low), the columnar structure 1 becomes aluminum quantum dots, and when the length L is larger than that, it becomes aluminum quantum wires.

  Further, the aluminum-containing columnar structures are separated from each other by a silicon region having silicon as a main component, as shown in FIG. That is, a plurality of columnar structures are dispersed in the silicon region.

  The columnar structures containing aluminum are preferably aligned in a specific direction. As shown in FIG.1 (b), it is good to align with the orthogonal | vertical direction especially with respect to a board | substrate.

  The substrate is not particularly limited, but an aluminum silicon mixture can be formed on an insulating substrate such as quartz glass, a silicon substrate, a semiconductor substrate such as gallium arsenide or indium phosphorus, or a substrate as a support member. If it is, a flexible substrate (for example, polyimide resin etc.) can also be used. Further, a substrate in which one or more films are formed on the support substrate may be used.

(Embodiment 4: Manufacturing method of aluminum silicon mixture)
This embodiment is applied to the manufacturing method of the aluminum silicon mixture of the third embodiment described above.

  A method for manufacturing an aluminum silicon mixture containing boron, nitrogen, hydrogen, or carbon according to the present invention will be described with reference to FIGS. Here, an example using a sputtering method is shown as a method for forming a film in a non-equilibrium state. In FIG. 2, 21 is a substrate and 22 is a sputtering target. When the sputtering method is used, the ratio of aluminum and silicon can be easily changed. Of course, boron or nitrogen can be included in the target as a compound of aluminum or silicon. Furthermore, it is also preferable that nitrogen, hydrogen, or the like is mixed in the sputtering gas to be contained in the mixture.

  As shown in FIG. 2, an aluminum silicon mixed film containing boron, nitrogen, hydrogen, or carbon is formed on a substrate by a magnetron sputtering method which is a film forming method for forming a substance in a non-equilibrium state.

  Silicon and aluminum as raw materials are achieved by disposing a silicon chip 23 on an aluminum target substrate as shown in FIG. In FIG. 2, the silicon chip 23 is divided into a plurality of parts. However, the present invention is not limited to this, and one silicon chip 23 may be provided as long as a desired film can be formed. However, in order to uniformly disperse a uniform aluminum-containing columnar structure in the silicon region, it is better to place it on the substrate 21. It is also possible to partially arrange silicon boride, silicon nitride, silicon hydride, and silicon carbide chips in the silicon chip 23.

  Alternatively, a fired aluminum silicon product obtained by firing a predetermined amount of boron, or aluminum or silicon powder containing nitrogen, hydrogen, or carbon can be used as the film forming target 22 material.

  Alternatively, a method of separately preparing an aluminum target and a silicon target and simultaneously sputtering both targets may be used. Further, the number of targets 22 may be increased to prepare a material containing boron, nitrogen, hydrogen, or carbon, and sputtering may be performed simultaneously.

  The amount of silicon in the film containing boron, nitrogen, hydrogen, or carbon to be formed is 0.30 ≦ x ≦ 0.80 with respect to the total amount of aluminum and silicon, preferably 0.35 ≦ x ≦ 0.75, and more preferably 0.40 ≦ x ≦ 0.70. Further, the contents of boron, nitrogen, hydrogen, and carbon are each preferably preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. Further, when boron, nitrogen, or hydrogen is used for controlling the conductivity type of the material, the amount satisfying y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ It is preferable to satisfy 0.995.

  The substrate temperature is 300 ° C. or lower, preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower. If the amount of silicon is within such a range, an aluminum silicon mixture in which columnar structures are dispersed in the silicon region can be obtained.

  When the aluminum silicon mixed film containing boron, nitrogen, hydrogen, or carbon is formed, the sample temperature is 300 ° C. or lower, preferably 200 ° C. or lower. As described above, the aluminum-silicon mixed film formed by forming the material in a non-equilibrium state between aluminum and silicon at a sample temperature of 300 ° C. or lower is a co-stable state of aluminum and silicon. A crystal structure is formed, and aluminum forms a nano-columnar structure having a level of several nanometers and is separated in a self-forming manner.

  The amount of silicon in the aluminum silicon mixture containing boron, nitrogen, hydrogen, or carbon can be controlled, for example, by changing the amount of silicon chips placed on the aluminum target. Furthermore, the boron, nitrogen, hydrogen, or carbon content can be varied as well.

  When film formation is performed in a non-equilibrium state, particularly in the case of sputtering, the pressure in the reaction apparatus when argon gas is flowed is preferably about 0.2 to 1 Pa, or 0.1 to 1 Pa. However, it is not particularly limited to this, and any pressure may be used as long as argon plasma is stably formed. That is, it is possible to perform sputtering in a low gas pressure region of 0.1 Pa or less, and it is also possible to use other rare gases as gas species. It is also preferable to partially mix nitrogen, hydrogen, and oxygen gas.

  Examples of the substrate 11 include a substrate such as an insulating substrate such as quartz glass, a semiconductor substrate such as silicon or gallium arsenide, and a substrate in which one or more layers are formed on these substrates. If there is no problem in forming the aluminum silicon nanomixture, the material, thickness, mechanical strength, etc. of the substrate are not particularly limited. In addition, the shape of the substrate is not limited to a flat plate shape, but includes a curved surface, a surface having a certain degree of irregularities and steps, and contains boron, nitrogen, hydrogen, or carbon. If there is no inconvenience in the aluminum silicon nanomixture, there is no particular limitation.

  A sputtering method is preferable as a film formation method for forming a substance in a non-equilibrium state, but a film formation for forming a substance in an arbitrary non-equilibrium state including resistance heating vapor deposition, electron beam vapor deposition (EB vapor deposition), and ion plating method. The law is applicable.

  As a film forming method, a simultaneous film forming process in which silicon and aluminum are simultaneously formed may be used, or a stacked film forming process in which silicon and aluminum are stacked in several atomic layers may be used.

(Embodiment 5: Aluminum silicon germanium mixture)
In this embodiment, the mixture of Embodiment 1 described above is applied to an aluminum silicon germanium mixture.

The case where aluminum is used as the first material constituting the columnar member and Si _z Ge _1-z (0 <z <1) is used as the second material will be described with reference to FIG. 1 again.

  FIG. 1A is a schematic plan view of a mixture 14 made of aluminum, silicon germanium containing boron, nitrogen, hydrogen, or carbon according to the present invention. FIG. 1B is a schematic cross-sectional view when the sample is cut along the broken line AA ′ in FIG. In FIG. 1, a region 11 mainly composed of the first material is aluminum, and a region 12 mainly composed of the second material is silicon germanium. In FIG. 1B, reference numeral 13 denotes a substrate.

  The film-like aluminum silicon germanium mixture 14 containing boron, nitrogen, hydrogen, or carbon formed on the substrate 13 has a total ratio of silicon and germanium to the total amount of 0.3 ≦ x ≦. It is preferably 0.8. Further, preferably 0.35 ≦ x ≦ 0.75, and more preferably 0.40 ≦ x ≦ 0.70. If the ratio of silicon germanium is within the above range, an aluminum silicon germanium mixture 14 in which columnar structures are dispersed in a region made of silicon germanium is obtained.

  The said ratio is a value when the quantity with respect to the total amount of silicon germanium and aluminum in the aluminum silicon germanium mixture film is quantitatively analyzed by, for example, inductively coupled plasma emission spectrometry. However, in the above ratio range, boron, nitrogen, hydrogen, or carbon is difficult to quantify relatively accurately, and thus does not exclude the occurrence of some fluctuation in the ratio. Further, the content of boron, nitrogen, hydrogen, or carbon with respect to aluminum and silicon germanium is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. Is preferred. In particular, when boron or nitrogen or hydrogen is used to control the conductivity type of the material when the second material is silicon or silicon germanium, an amount of y ≧ 0.995 is sufficiently controllable, For the purpose of imparting film hardness, y ≦ 0.995 is preferred.

Further, the composition ratio of silicon and germanium in the silicon germanium region constituting the silicon germanium mixed portion of the present invention is not particularly limited as long as at least both the silicon element and the germanium element are included. That is, when the composition ratio of silicon (Si) and germanium (Ge) is Si _z Ge ₁ -z, it is sufficient that the range is 0 <z <1. If the composition is within this range, the distance between the aluminum nanocolumnar structures can be controlled more widely than the control of the distance or diameter of the aluminum nanocolumnar structures that can be achieved with the aluminum silicon nanomixture or the aluminum germanium nanomixture. Is possible. In this sense, the present invention includes a method for controlling the interval and diameter between the columnar members.

  A mixture 14 of aluminum, silicon germanium containing boron, nitrogen, hydrogen, or carbon in the present invention has an aluminum columnar structure 11 having a composition containing aluminum as a main component, and silicon germanium around it as a main component. The silicon germanium region portion 12 is provided.

  The composition of the columnar structure 11 containing aluminum is mainly composed of aluminum, but if a fine mixture of columnar structures is obtained, silicon, germanium, boron, nitrogen, hydrogen, carbon, oxygen, Other elements such as argon may be contained. Note that the main component means that, for example, the ratio of aluminum in the component composition ratio of the columnar structure portion is 50 atomic% or more, and more preferably 80 atomic% or more.

  Further, the composition of the silicon germanium region portion 12 surrounding the columnar structure 11 is mainly composed of silicon and germanium, as long as it surrounds the fine mixture of the columnar structure containing aluminum. Various elements such as aluminum, boron, nitrogen, hydrogen, carbon, oxygen, and argon may be contained. Note that the main component is, for example, that the total ratio of silicon and germanium in the component composition ratio of the silicon germanium region is 50 atomic% or more, and more preferably 80 atomic% or more.

  The silicon germanium region 12 is preferably amorphous. In addition, it is preferable that the silicon germanium region 12 is amorphous silicon germanium from the viewpoint of insulation. The reason is that amorphous silicon germanium has a large band gap and high electrical insulation of the base material separating the columnar structures 11. Alternatively, in the region surrounding the columnar member by containing boron, nitrogen, hydrogen, or carbon, it is also preferable that a part of the crystalline material is present in the amorphous portion microscopically. In other words, the presence of the microcrystal is important because it is reflected in the electrical characteristics of the electronic device and the medium strength of the magnetic recording medium.

  The mixture 14 used here indicates a state in which aluminum is liberated in the silicon and germanium matrix.

  The columnar structure 11 containing aluminum has a circular shape or an elliptical shape as viewed from the film surface. Of course, as long as the columnar structures 11 are appropriately dispersed in the silicon germanium region 12, any shape may be employed.

  The diameter of the columnar structure 11 in the aluminum silicon germanium mixture 14 containing boron, nitrogen, hydrogen, or carbon according to the present invention is not particularly limited, but the average diameter is 0.5 nm or more and 30 nm. In the following, it is preferably 0.5 nm or more and 20 nm or less, more preferably 0.5 nm or more and 15 nm or less. The lower limit may be 1 nm or 2 nm. The diameter here is 2r in FIG. In the case of an ellipse or the like, the longest outer diameter portion may be within the above range. Here, the average diameter is, for example, a long axis when an aluminum portion observed in an SEM photograph (range of about 100 nm × 100 nm) of an actual film surface is imaged by a computer and the aluminum portion is assumed to be an ellipse. Is the average length derived as

  By the way, in a nanometer-sized nanomixture (approximately in the range of 0.1 nm to 100 nm), it becomes a size smaller than a certain characteristic length (mean free process, etc.), so that it has a unique electrical, optical, May show chemical properties. From such a viewpoint, the nanomixture is useful as a functional material, and also in the aluminum silicon germanium mixture according to the present invention, the diameter of the columnar structure constituting the mixture is 0.5 nm to 30 nm, particularly When it is 0.5 nm or more and 15 nm or less, various uses are possible as a nano mixture.

  The center-to-center distance 2R (FIG. 1 (b)) of the plurality of columnar structures is 30 nm or less, preferably 20 nm or less. Of course, the 2R has an interval at which the columnar structures do not contact each other. In particular, both the diameter 2r and the center-to-center distance 2R are preferably within the above ranges. Here, 2R can also be said to be the distance between the centers of adjacent columnar members.

  For example, the diameter of the aluminum nanostructure having a columnar structure is 1 to 15 nm, the interval of the aluminum nanomixture is 10 to 20 nm, and the ratio of the height and the diameter of the aluminum nanomixture is The fine mixture etc. which are 0.1-100,000 and the said aluminum nano mixture is perpendicular | vertical with respect to a board | substrate are mentioned.

  Further, the shape of the columnar structure 11 viewed from the cross section of the substrate may be a rectangular shape as shown in FIG. 1B, or an arbitrary shape such as a square or a trapezoid. The columnar structure includes a shape having an arbitrary aspect ratio (diameter / length). For example, the aspect ratio (diameter 2r / length L) can be 0.1 to 100,000.

  For example, the length L of the columnar structure can be applied in the range of 1 nm to 100 μm.

  In particular, consider a case where the length L is controlled in the range of 1 nm to several μm when the diameter 2r of the columnar structure is, for example, 1 to 15 nm and the center-to-center distance 2R is 10 to 20 nm. When the length L is several nanometers to several tens of nanometers (when the ratio of length to diameter is low), the columnar structure 1 acts as an aluminum quantum dot (0 dimension), and when the length L is larger than that, an aluminum quantum wire (1 Dimension).

  Further, the aluminum-containing columnar structures 11 are separated from each other by a silicon germanium region portion 12 containing silicon and germanium as main components, as shown in FIG. That is, a plurality of columnar structures are dispersed in the silicon germanium region.

  The aluminum-containing columnar structures 11 are preferably aligned in a specific direction. As shown in FIG.1 (b), it is good to align with the orthogonal | vertical direction especially with respect to a board | substrate.

  The substrate 13 is not particularly limited, but an insulating substrate such as quartz glass or plastic, a silicon substrate, a germanium substrate, a semiconductor substrate such as gallium arsenide, or indium phosphide, or aluminum on a substrate as a support member. If a silicon germanium mixture can be formed, a flexible substrate (such as a polyimide resin) can also be used. Further, a substrate in which one or more films are formed on the support substrate may be used.

(Embodiment 6: Manufacturing method of aluminum silicon germanium mixture)
This embodiment is applied to the manufacturing method of the aluminum silicon germanium mixture of the fifth embodiment described above.

  With reference to FIG. 2 again, a method for producing an aluminum silicon germanium mixture containing boron, nitrogen, hydrogen, or carbon according to the present invention will be described. Here, an example using a sputtering method is shown as a method for forming a film in a non-equilibrium state. In FIG. 2, 21 is a substrate and 22 is a sputtering target. When the sputtering method is used, the ratio of aluminum, silicon, and germanium can be easily changed by changing the target 22 material. Although 23 is described as a silicon chip, in this embodiment, it is a silicon chip or a germanium chip. Needless to say, boron, nitrogen, hydrogen, or carbon can be contained in the target as a compound of aluminum or silicon germanium. Furthermore, it is also preferable that nitrogen, hydrogen, or the like is mixed in the sputtering gas to be contained in the mixture.

  As shown in FIG. 2, an aluminum silicon germanium mixed film containing boron, nitrogen, hydrogen, or carbon is formed on a substrate by magnetron sputtering, which is a film forming method for forming a material in a non-equilibrium state. To do.

  As shown in FIG. 2, silicon, germanium, and aluminum as raw materials are formed by placing a silicon chip 23 and a germanium chip 23 on a target 22 made of aluminum, and a silicon, germanium boride, nitride, hydride, and carbide chip 23. It is achieved by arranging. In FIG. 2, these chips 23 are divided into a plurality of parts, but of course, the present invention is not limited to this. One chip 23 may be provided as long as a desired film formation is possible. However, in order to uniformly disperse the uniform aluminum-containing columnar structure in the silicon germanium region, it is better to place it on the substrate 21 as shown in FIG.

  Alternatively, a fired aluminum silicon germanium product obtained by firing a predetermined amount of boron, or powder of aluminum, silicon, or germanium containing nitrogen, hydrogen, or carbon can be used as a target material for film formation. By using such a target 22, it is possible to form a homogeneous film with little variation in film composition.

  Alternatively, a method of separately preparing an aluminum target, a silicon target, and a germanium target and simultaneously sputtering each target 22 may be used. At this time, boron, nitrogen, hydrogen, and carbon can be contained in the mixture by mixing in the target 22 as a boride, nitride, hydride, or carbide. Alternatively, a method in which nitrogen and hydrogen are partially mixed in the sputtering gas may be used.

  The total total amount of silicon and germanium in the formed film is 0.30 ≦ x ≦ 0.80, preferably 0.35 ≦ x ≦ 0.75, and more preferably, with respect to the total amount of aluminum, silicon, and germanium. Is 0.40 ≦ x ≦ 0.70. The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. In particular, when boron, nitrogen, or hydrogen is used to control the conductivity type of the material, an amount of y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ 0. .995 is preferred.

  The substrate temperature is 300 ° C. or lower, preferably 200 ° C. or lower, and preferably 100 ° C. or higher and 150 ° C. or lower. The lower limit is 0 ° C. or room temperature. If the total amount of silicon and germanium is produced within such a temperature range, boron in which columnar structures are dispersed in the silicon germanium region, or an aluminum silicon germanium mixture containing nitrogen, hydrogen, or carbon can be obtained. .

  The sample temperature when the aluminum, silicon germanium mixed film containing boron, nitrogen, hydrogen, or carbon is formed is 300 ° C. or lower, preferably 200 ° C. or lower. As described above, depending on the film formation conditions, boron, nitrogen, or nitrogen produced by forming a material in a non-equilibrium state of aluminum, silicon, and germanium at a sample temperature of 300 ° C. or less. Alternatively, an aluminum silicon germanium mixed film containing hydrogen or carbon has a metastable eutectic structure in which aluminum, silicon, and germanium are in a metastable state, and aluminum forms a nano-columnar structure with a level of several nanometers. Separate formally.

  The total amount of silicon and germanium in an aluminum silicon germanium mixture containing boron, nitrogen, hydrogen, or carbon can be changed, for example, by changing the amount of silicon chips or germanium chips placed on an aluminum target, or by combining aluminum, silicon and germanium. It can be controlled by using a target prepared by changing the amount of powder mixed.

  When film formation is performed in a non-equilibrium state, particularly in the case of sputtering, the pressure in the reaction apparatus when argon gas is flowed is preferably about 0.2 to 1 Pa, or 0.1 to 1 Pa. However, it is not particularly limited to this, and any pressure may be used as long as argon plasma is stably formed. That is, it is possible to perform sputtering in a low gas pressure region of 0.1 Pa or less, and it is also possible to use other rare gases as gas species. It is also preferable to partially mix nitrogen, hydrogen, and oxygen gas.

  Examples of the substrate 21 include a substrate such as an insulating substrate such as quartz glass, a semiconductor substrate such as silicon or gallium arsenide, and a substrate in which one or more layers are formed on these substrates. If there is no problem in forming the aluminum nanocolumnar structure, the material, thickness, mechanical strength, etc. of the base are not particularly limited. In addition, the shape of the substrate is not limited to a flat plate-like shape, but includes a curved surface, a surface having a certain degree of irregularities and steps, etc., but if there is no problem with the aluminum nanocolumnar structure, It is not particularly limited.

  The film forming method for forming the material in a non-equilibrium state is preferably a sputtering method, but the material is formed in any non-equilibrium state including a vapor deposition method (resistance heating vapor deposition, electron beam vapor deposition, etc.) and an ion plating method. A membrane method is applicable.

  As a method of film formation, a simultaneous film formation process in which silicon, germanium, and aluminum are simultaneously formed may be used, or a multilayer film formation process in which silicon, germanium, and aluminum are stacked in several atomic layers may be used. Absent.

(Embodiment 7: porous body)
This embodiment is applied to a porous body. The mixture applicable to the porous body of the present embodiment is the mixture described in the first, third, and fifth embodiments. And it is preferable to make it porous by removing the area | region 11 which has the 1st material of the mixture 14 in FIG. 1 as a main component.

  Referring to FIG. 3, the porous body 34 containing boron, nitrogen, hydrogen, or carbon of the present invention has a film surface with an average pore diameter 2r of 20 nm or less and an average interval 2R of 30 nm or less. The pores 31 are perpendicular or substantially perpendicular to each other, the pores 31 have a columnar diameter, and an aspect ratio (long) is a ratio of the length L of the pores 31 to the pore diameter 2r. (Thickness / pore diameter) is 0.1 to 10,000, and the pores 31 are separated by a silicon germanium region 32 mainly composed of silicon germanium containing boron, nitrogen, hydrogen, or carbon. Features.

  Further, FIG. 3A shows that the average pore diameter of the pores is 20 nm or less, and the average interval between the adjacent pores 31 is 30 nm or less, and the pores 31 are independent from each other and on the membrane surface. FIG. 3 is a schematic plan view that is perpendicular or nearly perpendicular to the surface. Moreover, FIG.3 (b) is typical sectional drawing when the porous body 34 is cut | disconnected along broken line BB 'of Fig.3 (a). In FIG. 3, 31 is a pore (nanohole), 32 is a region, 33 is a substrate, and 34 is a porous body.

  The porous body 34 according to this embodiment is characterized by being composed of pores 31 and regions 32. Further, as shown in FIG. 3B, the pores 31 are separated from each other, are independent without being connected to each other, and are formed perpendicular or substantially perpendicular to the substrate 33. Has been.

  Further, the shape of the pores 31 constituting the porous body 34 according to the present embodiment is a columnar shape as shown in FIG. Moreover, the pore diameter 2r (indicating the average pore diameter of the pore 31 as viewed from the membrane surface) 2r of the pore 31 is 20 nm or less, and the interval between the pores 31 (the average center interval of the pores 31 as viewed from the membrane surface) 2R is 30 nm or less. Preferably, the diameter 2r of the pore 31 is 0.5 to 15 nm, and the center distance 2R is 5 to 20 nm. The length L is in the range of 0.5 nm to several μm, preferably 2 nm to 5 μm.

  Here, “average pore diameter” means, for example, image processing (extraction) of a pore portion observed in an actual SEM photograph (a range of about 100 nm × 70 nm) by a computer, and image analysis assuming that the hole is an ellipse. It means the average of the long axis obtained.

  Further, as shown in FIG. 3B, the pores 31 in the porous body 34 can directly connect the pores 31 and the substrate 33, but the present invention is not limited to this. It is not necessary to connect the pores 31.

  The composition of the region 32 constituting the porous body 34 of the present embodiment is mainly composed of, for example, boron, nitrogen, hydrogen, or silicon germanium containing carbon, but from several to several tens atomic%. Various other elements such as aluminum (Al), oxygen (O), and argon (Ar) may be contained. Here, the content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. In particular, when boron, nitrogen, or hydrogen is used to control the conductivity type of the material, an amount of y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ 0. .995 is preferred.

  Further, the structure of the porous body 34 of the present embodiment is amorphous. Further, the shape of the pore 31 portion constituting the porous body 34 containing boron, nitrogen, hydrogen, or carbon of the present invention as viewed from the top surface of the substrate is substantially circular as shown in FIG. It may be of any shape, or may have any shape such as an ellipse. Furthermore, it is also preferable that a part of the amorphous part is crystalline.

  Further, the shape of the portion of the pore 31 constituting the porous body 34 of the present embodiment viewed from the cross section of the substrate may be a rectangular shape as shown in FIG. 3B, or an arbitrary shape such as a square or a trapezoid. But you can.

  Further, it is desirable that the aspect ratio (length / pore diameter), which is the ratio of the length L of the pores 31 to the pore diameter 2r, is 0.1 to 10,000, preferably 0.5 to 1,000.

(Embodiment 8: Silicon porous body)
In this embodiment, the porous body of Embodiment 7 described above is applied to a silicon porous body.

  The silicon porous body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a silicon porous body having columnar pores and a silicon region surrounding the pores, and an average of the pores A porous body having a pore diameter of 20 nm or less and an average interval between the pores of 30 nm or less.

The porous body is a film-shaped silicon porous body having a columnar-shaped pore and a silicon region made of silicon containing boron, nitrogen, hydrogen, or carbon, and the pore is on the film surface. The aspect ratio (length / pore diameter), which is a ratio between the pore length and the pore diameter, is 0.1 to 0.1 nm, the average pore diameter is 20 nm or less and the average interval is 30 nm or less. It is preferably 10,000 and the pores are separated by a silicon region containing silicon as a main component. An oxide film may be formed on the surface of the silicon region.
The average pore diameter of the pores is preferably 1 to 15 nm, and the average interval between the pores is preferably 5 to 20 nm.

  The silicon region preferably contains 80 atomic% or more of silicon. This ratio excludes the oxygen content. The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. In particular, when boron, nitrogen, or hydrogen is used to control the conductivity type of the material, an amount of y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ 0. .995 is preferred.

  The silicon is preferably amorphous silicon. Moreover, it is also preferable that a part of the amorphous part contains a crystalline substance.

(Embodiment 9: Germanium porous body)
In this embodiment, the porous body of Embodiment 7 described above is applied to a germanium porous body.

  The germanium porous body containing boron, nitrogen, or hydrogen according to the present embodiment is a germanium porous body having columnar pores and a germanium region surrounding the pores, and the pores have an average pore diameter. It is a porous body characterized by being 20 nm or less and having an average interval between the pores of 30 nm or less.

  The porous body is a film-like porous body having a germanium region whose main component is germanium containing columnar pores and boron, nitrogen, hydrogen, or carbon, and the pores are membranes. Provided perpendicular or nearly perpendicular to the surface, the average pore diameter of the pores is 20 nm or less, the average interval is 30 nm or less, and the aspect ratio (length / pore diameter), which is the ratio of the pore length to the pore diameter, is 0. It is preferably 1 to 10,000, and the pores are separated by a germanium region containing the germanium.

  The average pore diameter of the pores is preferably 1 to 15 nm, and the average interval between the pores is preferably 5 to 20 nm.

  The germanium region preferably contains 80 atomic% or more of germanium. This ratio excludes the oxygen content. The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. In particular, when boron, nitrogen, or hydrogen is used to control the conductivity type of the material, an amount of y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ 0. .995 is preferred.

  The germanium region preferably contains at least germanium and aluminum.

  The germanium is preferably amorphous germanium. Furthermore, it is preferable that a part of the amorphous is crystalline.

(Embodiment 10: Silicon germanium porous body)
In this embodiment, the porous body of Embodiment 7 described above is applied to a silicon germanium porous body.

  The silicon germanium porous body containing boron, nitrogen, or hydrogen according to this embodiment is a silicon germanium porous body having columnar pores and a silicon germanium region surrounding the pores, and an average of the pores The porous body has a pore diameter of 20 nm or less and an average interval between the pores of 30 nm or less.

  The porous body is a film-like porous body having a region containing silicon germanium containing columnar pores and boron, or nitrogen, hydrogen, or carbon, and the pores are on the membrane surface. The aspect ratio (length / pore diameter), which is a ratio between the pore length and the pore diameter, is 0.1 to 0.1 nm, the average pore diameter is 20 nm or less and the average interval is 30 nm or less. It is preferably 10,000 and the pores are separated by a silicon germanium region containing silicon germanium as a main component.

  The average pore diameter of the pores is preferably 1 to 15 nm, and the average interval between the pores is preferably 5 to 20 nm.

  The total amount of silicon and germanium in the silicon germanium region is preferably 80 atomic% or more. This ratio excludes the oxygen content. The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. In particular, when boron, nitrogen, or hydrogen is used to control the conductivity type of the material, an amount of y ≧ 0.995 is sufficiently controllable, and for the purpose of imparting film hardness, y ≦ 0. .995 is preferred.

When the composition ratio of silicon (Si) and germanium (Ge) in the silicon germanium region is Si _x Ge _{1 -x} , it is preferable that 0 <x <1.

  The silicon germanium is preferably amorphous silicon germanium. Furthermore, it is preferable that a part of the amorphous is crystalline.

(Embodiment 11: Manufacturing method of porous body)
This embodiment is applied to the porous body manufacturing method of Embodiment 7 described above.

  The method for producing a porous body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment includes a first material and a second material as main components, and boron, nitrogen, or hydrogen, Alternatively, a step of preparing a carbon-containing mixture in which a columnar member including the first material is surrounded by a region including the second material (FIG. 4 (a)), and a step of removing the columnar member from the mixture (see FIG. 4 (b)).

  In FIG. 4, 41 is a region mainly composed of the first material, 42 is a region mainly composed of the second material arranged so as to surround the region mainly composed of the first material, and 43 is mixed. The body, 44 is a substrate, 45 is a porous body, and 46 is a pore.

  Here, the mixture 43 preferably contains the second material in a ratio of 0.3 ≦ x ≦ 0.8. However, the ratio is not limited to the above as long as the mixture 43 in which the columnar structures aligned in the vertical direction on the substrate 44 are dispersed in the region is obtained. In the present invention, it is important that the mixture 43 is obtained by a combination of materials that can selectively remove the columnar structure from the mixture. Further, boron, nitrogen, hydrogen, or carbon may be mixed from the first material, the compound of the second material, or a mixture. In the sputtering method, it is introduced into a part of a gas such as argon. It is also preferable to achieve this.

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.7 ≦ y ≦ 0.995.

  In addition, after the formation of the pores 46, the pores 46 can be enlarged as necessary (see FIG. 4C).

  As the first material, for example, aluminum or gold can be used, and as the second material, for example, Si, SiGe, Ge, C, or a combination thereof can be used. Of course, a plurality of types of materials may be combined. The same applies to the following description.

  The method for producing a porous body containing boron, nitrogen, hydrogen, or carbon according to the present invention has the following steps (a) to (c).

  (A) Step: A first material (for example, aluminum) and a second material (for example, silicon) are prepared.

  (B) Step: Next, the two materials are formed on the substrate by using a film forming method in which substances are formed in a non-equilibrium state. A mixture containing boron, nitrogen, hydrogen, or carbon obtained by the film formation includes a columnar member including the first material and the second material, and surrounds the columnar member. And having a region. A mixture in which columnar members are dispersed by forming a film so as to contain the second material in a ratio of 0.3 ≦ x ≦ 0.8 with respect to the total amount of the first material and the second material. Is obtained. Of course, in order to contain boron, nitrogen, hydrogen, or carbon, a method of mixing the first material or the second material as a compound or mixture is preferable. Furthermore, when using the sputtering method, a method achieved by introducing nitrogen or hydrogen gas into part of the argon gas is also preferable.

  Step (c): Next, columnar members are removed from the obtained mixture to form pores. When wet etching is performed using an acid or an alkali that easily dissolves the first material as compared to the second material, columnar members mainly formed of the first material are removed to form pores.

The columnar member may be removed by etching or the like as long as the columnar member is substantially selectively removed, and it is not necessary to remove the entire length of the columnar member in the depth direction.
In addition, following the step (c), wet etching using an acid or alkali that dissolves the second material can be performed to widen the pore diameter of the formed pores.

  Also in this step, boron, nitrogen, hydrogen, or carbon can be contained, and ionized boron or the like can be implanted by an ion implantation method. Of course, although the amount to be mixed is small, it is sufficiently applicable from the viewpoint of doping.

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  Furthermore, the manufacturing method of the porous body which concerns on this invention is demonstrated later on in order of (a)-(d).

  (A) Process: A first material (for example, aluminum) and a second material (for example, silicon) are prepared in a film forming apparatus. At this time, when boron, nitrogen, hydrogen, or carbon is contained, it is preferably contained in advance as a compound or mixture in the first material or the second material.

  For example, as shown in FIG. 2, a chip made of a second material (for example, silicon) is disposed on a target (substrate) made of a first material (for example, aluminum).

  Alternatively, a second or first material chip containing boron, nitrogen, hydrogen, or carbon is placed on a target made of the first material or the second material.

(B) Step: Formation of Mixture Next, the mixture is formed on the substrate. Here, an example in which a sputtering method is used as a film formation method for forming a substance in a non-equilibrium state is shown.
A mixture is formed on the substrate by magnetron sputtering, which is a film forming method for forming a substance in a non-equilibrium state. The mixture is composed of a columnar member made of a composition containing the first material as a main component and a region arranged around it and containing the second material as a main component.

  As shown in FIG. 2, a mixture is formed on the substrate 21 by a magnetron sputtering method which is a film forming method for forming a substance in a non-equilibrium state.

  The second material and the first material as the raw material are achieved by arranging the chip 23 made of the second material on the target 22 including the first material as shown in FIG. In FIG. 2, the chip 23 is divided into a plurality of chips. However, the present invention is not limited to this, and one chip 23 may be used as long as a desired film can be formed. However, in order to uniformly disperse the columnar members in the region, it is preferable to arrange them on the substrate 21.

In addition, a fired product obtained by firing a predetermined amount of powder of a first material (for example, aluminum) and a second material (for example, silicon) can be used as a target material for film formation.
Further, for example, a method of separately preparing an aluminum target and a silicon target and simultaneously sputtering both targets 22 may be used.

  Further, in addition to a method in which the target 22 contains boron, nitrogen, hydrogen, or carbon, a method in which part of argon as a sputtering gas is changed to nitrogen or hydrogen is also preferable.

  The amount of the second material in the formed film is a ratio of 0.3 ≦ x ≦ 0.8 with respect to the total amount of the first material and the second material, and preferably 0.35 ≦ x ≦ It is 0.75, More preferably, it is 0.40 <= x <= 0.70. When the amount of the second material is within such a range, a mixture in which columnar members are dispersed in the region is obtained.

  Further, the substrate temperature is 300 ° C. or lower, preferably 200 ° C. or lower.

  When the mixture is formed by such a method, the first material and the second material become a metastable eutectic structure, and the first material is in the matrix formed by the second material. A nano-mixture (columnar member) of several nm level is formed and separated in a self-organized manner. The columnar member at that time has a substantially columnar shape, the hole diameter is 1 to 20 nm, and the interval is 5 to 30 nm.

  The amount of the second material contained in the mixture can be controlled, for example, by changing the amount of chips placed on the target made of the first material.

  When film formation is performed in a non-equilibrium state, particularly in the case of sputtering, the pressure in the reaction apparatus when argon gas is flowed is preferably about 0.2 to 1 Pa, or about 0.1 to 1 Pa.

  Further, sputtering in a low gas pressure region of 0.1 Pa or less may be used, and other rare gases may be used as gas species, and it is also preferable to partially mix nitrogen, hydrogen, oxygen, or the like.

  The output for forming plasma is preferably about 150 to 1000 W for a 4-inch target. However, the present invention is not particularly limited to this, and any pressure and output may be used as long as argon plasma is stably formed.

  As the substrate, for example, an insulating substrate such as quartz glass or plastic, a semiconductor substrate such as silicon or gallium arsenide, a metal substrate, a carbon substrate, or one or more layers on these substrates. What was formed is mentioned. In addition, as long as there is no problem in forming the mixture according to the present invention, the material, thickness, mechanical strength, etc. of the substrate are not particularly limited. In addition, the shape of the substrate is not limited to a flat plate shape, but includes a curved surface, a surface having a certain degree of unevenness or a step, and the like. It is not something. A flexible substrate using a polyimide resin or the like can also be used. In the case of a silicon substrate, a p-type, n-type, high resistance or low resistance substrate can be used.

  A sputtering method is preferable as a film forming method for forming a substance in a non-equilibrium state, but a film forming method for forming a substance in any non-equilibrium state such as resistance heating vapor deposition and electron beam vapor deposition (EB vapor deposition) can be applied. is there. Note that, among the sputtering methods, it is also preferable to perform sputtering in a state where plasma is not substantially in contact with the substrate on which the mixture is grown.

In addition, as a method of film formation, a simultaneous film formation process in which the first material and the second material are simultaneously formed may be used, or a multilayer film formation process in which both materials are stacked in several atomic layers may be used. Good.
The mixture formed as described above includes a columnar member made of a composition mainly composed of the first material and a silicon region mainly composed of the second material around it.

  The composition of the columnar member portion is mainly composed of the first material, but may contain other elements such as silicon, oxygen, and argon as long as a fine mixture having a columnar structure is obtained. . The main component is, for example, a ratio of aluminum in the component composition ratio of the columnar member portion of 80 atomic% or more, preferably 90 atomic% or more. The oxygen content is excluded from this ratio.

  The composition of the region surrounding the columnar member is mainly composed of the second material. However, if a fine mixture having a columnar structure is obtained, it contains a large amount of boron, nitrogen, hydrogen, and carbon. However, it is preferable to include it in the ratio of y ≧ 0.7. Moreover, you may contain various elements, such as aluminum, oxygen, and argon. The main component is, for example, the ratio of the second material in the component composition ratio of the region 24 is 80 atomic% or more, or 90 atomic% or more.

(C) Process: pore formation process The columnar member in the said mixture is selectively removed. As a result, a region having pores remains in the mixture, and a porous body is formed.

  The pores in the silicon porous body containing boron, nitrogen, hydrogen, or carbon have an interval 2R of 30 nm or less and a pore diameter 2r of 20 nm or less. Preferably, the pore diameter 2r of the pore is 1 -15 nm, and the interval 2R is 5-20 nm. The length L is in the range of 0.5 nm to several μm, preferably 2 nm to 1000 nm.

  Examples of the solution used for etching include acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and chromic acid solution that dissolve aluminum and hardly dissolve silicon, but if there is no problem in forming pores by etching, an alkali such as sodium hydroxide is used. Is not particularly limited to the type of acid or the type of alkali. Also, a mixture of several types of acid solutions or several types of alkali solutions may be used. Etching conditions can be set as appropriate according to the silicon porous body containing boron, nitrogen, hydrogen, or carbon to be produced, for example, the solution temperature, concentration, and time. Of course, etching using alkali is also preferable because etching resistance is improved by containing boron, nitrogen, hydrogen, or carbon.

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  An oxide film can be formed on the pore wall of the porous body obtained by the above process.

  Moreover, you may perform the following processes (d) as needed.

(D) Process: pore diameter expansion process:
Further, the porous material is appropriately finely treated by pore wide treatment in which it is immersed in an acid solution that dissolves the second material, such as a solution diluted with hydrogen fluoride, or an alkaline solution such as sodium hydroxide. The hole diameter can be increased. Any acid and alkali may be used for this solution as long as there is no problem in pore enlargement. Also, a mixture of several types of acid solutions or several types of alkali solutions may be used.

  In addition, the pore diameter enlargement (pore wide treatment) conditions can be appropriately set according to the size of the pores to be produced, for example, the solution temperature, concentration, and time.

(Embodiment 12: Silicon porous body production method)
This embodiment is applied to the silicon porous body manufacturing method of the eighth embodiment described above.

  The method for producing a porous silicon body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a mixture including aluminum and silicon, and includes a columnar member including aluminum and the columnar shape. And a step of preparing an aluminum silicon mixture containing silicon in a ratio of 0.3 ≦ x ≦ 0.8 with respect to the total amount of aluminum and silicon, and the silicon silicon mixture And a step of removing the columnar member containing aluminum.

  The porous body manufacturing method includes: (a) a step of preparing aluminum and silicon; (b) a columnar member containing aluminum by using a film forming method of forming a material in a non-equilibrium state of the aluminum and silicon; Forming a silicon region surrounding the columnar member, and forming an aluminum silicon mixture containing silicon, boron, nitrogen, hydrogen, or carbon in a ratio of 0.3 ≦ x ≦ 0.8, And (c) preferably, a step of etching the aluminum of the aluminum silicon mixture to form pores.

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  The etching is preferably wet etching using acid or alkali.

  The method for producing a porous body containing boron, nitrogen, hydrogen, or carbon includes (a) a step of preparing aluminum and silicon, and (b) a step of forming a material in a non-equilibrium state of the aluminum and silicon. Using a film method, it has a columnar member containing aluminum and a silicon region surrounding the columnar member, and silicon contains boron, nitrogen, or hydrogen in a ratio of 0.3 ≦ x ≦ 0.8. Preferably, the method includes a step of forming an aluminum silicon mixture, (c) a step of etching aluminum of the aluminum silicon mixture to form pores, and (d) a step of widening the pore diameter.

The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.80 ≦ y ≦ 0.995.
The step of expanding the pores is preferably wet etching using acid or alkali.

  The film forming method for forming the substance in the non-equilibrium state is preferably a sputtering method.

(Embodiment 13: Method for producing porous germanium)
The present embodiment is applied to the method for manufacturing a germanium porous body of the ninth embodiment described above.

  A method for producing a porous germanium containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a mixture including aluminum and germanium, and includes a columnar member including aluminum and the columnar A germanium region surrounding the member, and preparing a germanium mixture containing germanium in a ratio of 0.30 ≦ x ≦ 0.80 containing boron, nitrogen, hydrogen, or carbon, and It has the process of removing the columnar member containing this aluminum from an aluminum germanium mixture.

  The method for producing a porous body containing boron, nitrogen, hydrogen, or carbon includes (a) a step of preparing aluminum and germanium, and (b) a method of forming a substance in a non-equilibrium state of the aluminum and germanium. Using a film method, a columnar member containing aluminum and a germanium region surrounding the columnar member, and germanium in a ratio of 0.30 ≦ x ≦ 0.80, boron, nitrogen, hydrogen, or It is preferable to have a step of forming an aluminum germanium mixture containing carbon, and (c) a step of etching the aluminum of the aluminum germanium mixture to form pores.

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  The etching is preferably wet etching using acid or alkali.

The manufacturing method of the porous body containing boron, nitrogen, or hydrogen includes (a) a step of preparing aluminum and germanium, and (b) a film forming method of forming a material in a non-equilibrium state of the aluminum and germanium. And having a columnar member containing aluminum and a germanium region surrounding the columnar member, and containing germanium in a ratio of 0.30 ≦ x ≦ 0.80, boron, nitrogen, hydrogen, or carbon It is preferable to include a step of forming an aluminum germanium mixture, (c) a step of etching aluminum of the aluminum germanium mixture to form pores, and (d) a step of expanding the pore diameter of the pores.
The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.80 ≦ y ≦ 0.995.

  The step of expanding the pores is preferably wet etching using acid or alkali.

  The film forming method for forming the substance in the non-equilibrium state is preferably a sputtering method.

(Embodiment 14: Method for producing silicon germanium porous body)
This embodiment is applied to the silicon germanium porous body manufacturing method of the ninth embodiment described above.

  The method for producing a silicon germanium porous body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a mixture including aluminum, silicon, and germanium, and a columnar member including aluminum And a silicon germanium region surrounding the columnar member, and a total amount of silicon and germanium in a ratio of 0.30 ≦ x ≦ 0.80 containing boron, nitrogen, hydrogen, or carbon It has the process of preparing a mixture, and the process of removing the columnar member containing this aluminum from this aluminum silicon germanium mixture.

  The method for producing a porous body containing boron, nitrogen, hydrogen, or carbon includes (a) a step of preparing aluminum, silicon, and germanium, and (b) a substance in a non-equilibrium state of the aluminum, silicon, and germanium. A columnar member containing aluminum and a silicon germanium region surrounding the columnar member, and the total amount of silicon and germanium is 0.30 ≦ x ≦ 0.80, Preferably, the method includes a step of forming an aluminum silicon germanium mixture containing boron, nitrogen, hydrogen, or carbon, and (c) a step of etching the aluminum of the aluminum silicon germanium mixture to form pores. .

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.7 ≦ y ≦ 0.995.

  The etching is preferably wet etching using acid or alkali.

  The method for producing a porous body containing boron, nitrogen, or hydrogen includes (a) a step of preparing aluminum, silicon, and germanium, and (b) forming a material in a non-equilibrium state of the aluminum, silicon, and germanium. Using a film forming method, a columnar member containing aluminum and a silicon germanium region surrounding the columnar member, the total amount of silicon and germanium being boron at a ratio of 0.30 ≦ x ≦ 0.80, or Forming an aluminum silicon germanium mixture containing nitrogen, hydrogen, or carbon; and (c) etching the aluminum of the aluminum silicon germanium mixture to form pores; and (d) the pores. It is preferable to have a step of expanding the pore diameter.

  The content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.7 ≦ y ≦ 0.995.

  The step of expanding the pores is preferably wet etching using acid or alkali.

  The film forming method for forming the substance in the non-equilibrium state is preferably a sputtering method.

The following Embodiments 15 to 20 are reference examples.
(Embodiment 15: oxide porous body)
This embodiment is applied to an oxide porous body. The mixture applicable to the porous oxide body of the present invention is the mixture described in the first embodiment. And it is preferable to make it porous by removing the 1st material of the mixture which can be applied.

  That is, the porous oxide body according to the present embodiment includes a removal treatment for removing the columnar member made of the first material from the mixture containing boron, nitrogen, hydrogen, or carbon, and an oxidation treatment step. It is obtained by including. These two processes may be performed simultaneously with the removal process, may be performed after the removal process, or may be performed after the oxidation process. The term “simultaneous” here does not need to be strictly coincident in terms of time, and includes, for example, a case where the substrate subjected to the removal step by etching is oxidized as a result. In addition, boron, nitrogen, and hydrogen can be mixed at the time of preparing the mixture, but a method of heating or plasma treatment in an atmosphere of nitrogen gas, ammonia gas, or hydrogen gas after the removing step by etching is also preferable.

  In the present embodiment, examples of the first material include Al, Au, Mg, and Ag. Examples of the second material include Si, Ge, SixGe1-x and the like. In particular, the second material is desirably a material that can be amorphous.

  The first and second materials are preferably materials having eutectic points (so-called eutectic materials) in both component phase equilibrium diagrams. In particular, the eutectic point is 300 ° C. or higher, preferably 400 ° C. or higher. A eutectoid system can also be used as the first and second materials. As a preferable combination as the first material and the second material, Al is used as the first material, Si is used as the second material, Al is used as the first material, and the second material is used as the second material. It is preferable to use Ge as the first material or Al as the first material and SixGe1-x (0 <x <1) as the second material.

  In addition, it is preferable that it is 1 atomic% or more and 20 atomic% or less as a ratio of the 1st material (for example, aluminum) contained in the said area | region which comprises a porous body. Here, the oxygen content contained in the porous body is not considered in the above ratio.

  The region surrounding the columnar member is preferably amorphous. Furthermore, it is also preferable that the amorphous part partially contains crystalline.

  The planar shape of the columnar member is circular or elliptical.

  By removing the columnar member from the mixture (wet etching or dry etching), a porous body having a plurality of columnar holes is formed. For the etching, it is only necessary to selectively remove the columnar member, and as the etchant, for example, acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid are suitable. It is preferable that the pores of the porous body formed by the removal are independent without being connected to each other. When the porous body is oxidized or the like, the mixture having pores may be completely oxidized, or the pore wall may be mainly oxidized to leave the non-oxidized portion inside the pore wall. .

  The porous body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment includes a plurality of columnar holes and a region surrounding the hole, and the region includes Si, Ge, or a combination thereof. The oxide is an amorphous region.

  In FIG. 5A, 51 is a pore and 52 is an oxide region (for example, formed of Si, Ge, or a combination thereof) surrounding the pore. 53 is a substrate, and 54 is an oxide porous body.

  FIG.5 (b) is typical sectional drawing when a porous body is cut | disconnected along broken line CC 'of Fig.5 (a).

  As shown in FIG. 5B, according to this embodiment, an oxide porous body 54 having pores 51 that are not substantially branched is obtained. As is clear from the figure, the pores 51 are independent of each other, and the pores 51 perpendicular to or substantially perpendicular to the film surface (or substrate) can be obtained.

  According to this embodiment, the average center-to-center distance (2R in FIG. 1) between the plurality of pores 51 is 30 nm or less, and the average diameter of the columnar pores 51 is 20 nm or less (2r in FIG. 1). be able to. Preferably, the diameter 2r of the pore 51 is 0.5 to 15 nm, and the distance 2R between the centers is 5 to 20 nm. The length L is in the range of 0.5 nm to several μm, preferably 2 nm to 5 μm. Here, the average pore diameter is, for example, image processing (extraction) of a pore portion observed in an actual SEM photograph (a range of about 100 nm × 100 nm) by a computer, and image analysis assuming that the hole is an ellipse. It means the average of the major axis obtained.

  Further, as shown in FIG. 5B, the pore 51 in the porous oxide body 54 according to the present embodiment can directly connect the pore 51 and the substrate 53, but is not limited thereto. The substrate 53 and the pore 51 may not be connected.

  The composition of the oxide region 52 constituting the oxide porous body according to the present embodiment is mainly composed of an oxide of a second material containing boron, nitrogen, hydrogen, or carbon. However, it may contain other elements such as aluminum (Al), argon (Ar), etc., from several to several tens atomic%. Further, the content of boron, nitrogen, or hydrogen is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  In particular, when a columnar member including the above-described first material such as aluminum is present at a position where the columnar pores 51 are present, aluminum or the like is present in the oxide porous body 54. . The concentration of the first material constituting the columnar member is high in the vicinity of the porous hole wall surface, and is low in the hole wall. That is, the first material in the oxide porous body 54 has a concentration distribution in the in-plane direction. Of course, if the diffusion of the first material such as aluminum is promoted by heat treatment or the like, the concentration distribution decreases.

  Note that the porous oxide body 54 containing boron, nitrogen, hydrogen, or carbon has an amorphous structure both near and inside the pore wall surface. It is also preferable that a part of the crystalline material is formed in the amorphous part.

The second material is Si, SiGe, Ge, or a combination material thereof.
Further, the structure of the region 2 constituting the porous oxide body 54 according to the present embodiment is an amorphous structure, and the shape of the pore 51 portion viewed from the top surface of the substrate is as shown in FIG. In addition, it may be substantially circular, or may have an arbitrary shape such as an ellipse.

  Further, the shape of the pore 51 portion constituting the oxide porous body 54 of the present embodiment viewed from the cross section of the substrate may be a rectangular shape as shown in FIG. 5B, or an arbitrary shape such as a square or a trapezoid. It may be. Further, it is preferable that the depth directions of the plurality of pores 51 are substantially the same.

  The oxide region 52 may contain aluminum.

  According to the present embodiment, the aspect ratio (length / pore diameter), which is the ratio of the length of the pore 51 to the pore diameter, can be set to 0.1 to 10,000.

  The porous oxide body 54 according to the present invention is a film-like mixture having columnar pores 51 and oxide regions 52, and the pores 51 are perpendicular or almost perpendicular to the membrane surface. Provided, the average pore diameter of the pores 51 is 20 nm or less, the average interval is 30 nm or less, and the pores 51 are separated by an oxide region 52.

  The pores 51 are separated from each other by oxide regions 52 as shown in FIG. 5B, are independent of each other, and are perpendicular to or substantially perpendicular to the substrate 53. It is formed vertically.

  Further, the shape of the pores 51 constituting the porous oxide body 54 containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is as shown in FIG. It is a columnar shape. The pore diameter (indicating the average pore diameter) 2r of the pores 51 is 20 nm or less, and the interval (indicating the average interval) 2R between the pores 51 is 30 nm or less. Preferably, the diameter 2r of the pores 51 is 1 to 15 nm, and the interval 2R is 5 to 20 nm. The length L is in the range of 5 nm to several μm, preferably 2 nm to 1000 nm. Here, “average pore diameter” means, for example, image processing (extraction) of a pore portion observed in an actual SEM photograph (a range of about 100 nm × 100 nm) by a computer, and image analysis assuming that the hole is an ellipse. It means the average of the long axis obtained.

  Further, the pore 51 in the porous oxide body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment directly connects the pore 51 and the substrate 53 as shown in FIG. However, the present invention is not limited to this, and the substrate 53 and the pore 51 may not be connected.

Further, when the oxide porous body 54 containing boron, nitrogen, hydrogen, or carbon according to the present embodiment contains silicon oxide (SiO _x ) as a main component, boron, nitrogen, hydrogen, or The carbon content is preferably y ≧ 0.7, more preferably 0.8 ≦ y ≦ 0.995. In addition to oxides such as aluminum oxide (AlO _x ), various elements such as argon (Ar) may be contained. The silicon (Si) content in the silicon oxide region is 80 atomic% or more, preferably 85 to 99 atomic%, with respect to all elements except oxygen.

  In addition, when aluminum is used as the first material, the content of aluminum contained in the obtained oxide porous body 54 is in the range of 0.01 to 20 atomic% with respect to all elements except oxygen. The range is preferably from 0.1 to 10 atomic%.

  The columnar shape of the pore 51 includes a shape having an arbitrary aspect ratio (length L / pore diameter 2r) as long as the size is satisfied. The aspect ratio (length L / hole diameter 2r) is preferably in the range of 0.5 to 1000.

(Embodiment 16: Silicon oxide porous body)
In the present embodiment, the porous oxide body according to the fifteenth embodiment is applied to a porous silicon oxide body.

  The silicon oxide porous body containing boron, nitrogen, hydrogen, or carbon according to this embodiment is a silicon oxide porous body having columnar pores and a silicon oxide region surrounding the pores. The porous oxide body is characterized in that the average pore diameter of the pores is 20 nm or less and the average interval between the pores is 30 nm or less.

  A film-like silicon oxide porous body having a columnar-shaped pore and a silicon oxide region mainly composed of silicon oxide containing boron, nitrogen, hydrogen, or carbon, wherein the pore A silicon oxide region provided perpendicularly or substantially perpendicularly to the membrane surface, having an average pore diameter of 20 nm or less and an average interval of 30 nm or less, and wherein the pores are composed of the silicon oxide as a main component. Preferably they are separated.

  The average pore diameter of the pores is preferably 1 to 15 nm, and the average interval between the pores is preferably 5 to 20 nm.

  The silicon oxide region preferably contains 80 atomic% or more of silicon with respect to the total amount of all elements except oxygen.

  In the silicon oxide containing boron, nitrogen, hydrogen, or carbon, the content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, more preferably 0.8 ≦ y. It is preferable that ≦ 0.995. Furthermore, it is preferable that an aluminum oxide is included. Further, the silicon oxide containing boron, nitrogen, hydrogen, or carbon is preferably amorphous. Moreover, it is preferable that a part of amorphous part is crystalline.

(Embodiment 17: germanium oxide porous body)
In the present embodiment, the porous oxide body according to the fifteenth embodiment is applied to a porous germanium oxide body.

  The germanium oxide porous body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a germanium oxide porous body having columnar pores and a germanium oxide region surrounding the pores. The porous oxide body is characterized in that the average pore diameter of the pores is 20 nm or less and the average interval between the pores is 30 nm or less.

  A porous germanium film having a columnar shape and a germanium oxide region mainly composed of a germanium oxide containing boron, nitrogen, hydrogen, or carbon, wherein the pores are A germanium oxide region provided perpendicularly to or substantially perpendicular to the membrane surface, having an average pore diameter of 20 nm or less and an average interval of 30 nm or less, and wherein the pores are composed of the germanium oxide as a main component; Preferably they are separated.

  The average pore diameter of the pores is preferably 1 to 15 nm, and the average interval between the pores is preferably 5 to 20 nm.

  The germanium oxide region preferably contains 80 atomic% or more of germanium with respect to the total amount of all elements except oxygen. Further, the content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  The germanium oxide region containing boron, nitrogen, hydrogen, or carbon preferably contains aluminum oxide. Further, the germanium oxide containing boron, nitrogen, hydrogen, or carbon is preferably amorphous. Moreover, it is preferable that a part of amorphous part is crystalline.

(Embodiment 18: Silicon germanium oxide porous body)
In this embodiment, the porous oxide body according to the fifteenth embodiment described above is applied to a porous silicon germanium oxide body.

  The silicon germanium oxide porous body containing boron, nitrogen, hydrogen, or carbon according to this embodiment is a silicon germanium oxide porous body having columnar pores and a silicon germanium oxide region surrounding the pores. The porous porous body is characterized in that the average pore diameter of the pores is 20 nm or less and the average interval between the pores is 30 nm or less.

  A film-like silicon germanium oxide porous body having a silicon germanium oxide region mainly composed of silicon germanium oxide containing columnar pores and boron, or nitrogen, hydrogen, or carbon, The pores are provided perpendicularly or substantially perpendicular to the membrane surface, the pores have an average pore diameter of 20 nm or less and an average interval of 30 nm or less, and the pores are boron, nitrogen, hydrogen, or carbon It is preferable to be separated by a silicon germanium oxide region mainly containing silicon germanium oxide containing.

  The average pore diameter of the pores is preferably 1 to 15 nm, and the average interval between the pores is preferably 5 to 20 nm.

  The silicon germanium oxide region preferably contains 80 atomic% or more of the total of silicon and germanium with respect to the total amount of all elements except oxygen. Further, the content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

When the ratio of the composition of silicon element (Si) and germanium element (Ge) in the silicon germanium oxide region containing boron, nitrogen, hydrogen, or carbon is Si _z Ge _1-z , 0 <z < A range of 1 is preferred. The silicon germanium oxide containing boron, nitrogen, hydrogen, or carbon preferably contains aluminum oxide.

  The silicon germanium oxide is preferably amorphous. Furthermore, it is preferable that a part of the amorphous portion contains crystalline.

(Embodiment 19: Method for producing oxide porous body)
This embodiment is applied to the oxide porous body manufacturing method of Embodiment 15 described above. Hereinafter, the manufacturing method of the porous oxide body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment will be described in detail.

  The method for producing an oxide porous body according to the present embodiment is a mixture including a first material and a second material, and a columnar member including the first material includes: A step of preparing a mixture surrounded by a region including the second material (see FIG. 6A), and a removing step of removing the columnar member from the mixture (FIG. 6B) And a step of oxidizing the region.

  In FIG. 6, 61 is a region mainly composed of the first material, 62 is a substrate, 63 is a mixture, 64 is a region mainly composed of the second material, 65 is a porous body, 66 is a pore, Reference numeral 67 denotes expanded pores and 68 oxide porous body.

  Here, the mixture 63 may contain the second material in a ratio of 0.30 ≦ x ≦ 0.80. However, the ratio is not limited to the above as long as a mixture in which the columnar structures arranged in the vertical direction on the substrate 62 are dispersed in the region is obtained. In the present embodiment, it is important that the mixture 63 is obtained by a combination of materials that can selectively remove the columnar structure from the mixture.

  In addition, after the said removal process, the hole diameter expansion process which expands the hole diameter of the oxide porous body 68 can also be performed as needed (refer FIG.6 (d)). Of course, after the removing step, the oxidizing step may be performed after the pore diameter expanding step without performing the oxidizing step.

  In order to contain boron, nitrogen, hydrogen, or carbon, a columnar member that includes the first material is surrounded by a region that includes the second material. Means such as mixing in the step of preparing the body, implanting ions into the film by ion implantation thereafter, or performing heat treatment or plasma treatment in a gas made of the material to be mixed are preferable. Further, the content of boron, nitrogen, hydrogen, or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

  As the first material, for example, aluminum or gold can be used, and as the second material, for example, Si, SiGe, Ge, or a combination thereof can be used. Of course, a plurality of types of materials may be combined. The same applies to the following description.

  Below, the process regarding the manufacturing method of an oxide porous body is divided and demonstrated to (a)-(d).

  (A) Step: First, a first material (for example, aluminum) and a second material (for example, silicon) are prepared. If boron, nitrogen, hydrogen, or carbon is contained at this point, boron, nitrogen, hydrogen, or carbon is adjusted to the target composition as a compound or mixture in the first material or the second material. It is preferable to mix them.

  Step (b): Next, a mixture is formed on the substrate using a film forming method in which the first material and the second material are formed in a non-equilibrium state (see FIG. 6A). . The mixture obtained by film formation includes a columnar member including the first material and a region that is formed of the second material and surrounds the columnar member. By forming a film so as to contain the second material in a ratio of 0.30 ≦ x ≦ 0.80, a mixture in which columnar members are dispersed is obtained. In particular, when boron, nitrogen, hydrogen, and carbon are mixed in the raw material in advance, it can be taken into the mixture at this point.

  (C) Step: Next, the columnar member is removed from the mixture by etching or the like to form pores (see FIG. 6B). When wet etching using acid or alkali is performed on the mixture, the columnar member is selectively removed to form a porous body having pores.

  Step (d): Next, the porous body having the pores is oxidized to obtain an oxide porous body (see FIG. 6C).

  Subsequent to the step (d), the step (e) of expanding the pore diameter of the oxide porous body by performing wet etching using an acid or alkali may be performed.

  In the oxidation step, heat treatment in an oxygen atmosphere and plasma treatment can be applied. However, when mixing of boron, nitrogen, hydrogen, and carbon has not yet been achieved, heat treatment is performed particularly in nitrogen and hydrogen. The addition to the mixture can be performed by plasma treatment.

  The manufacturing method of the porous oxide body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment includes the following steps (a) to (c), (e ′), and (d). Features.

  (A) Step: First, a first material (for example, aluminum) and a second material (for example, silicon) are prepared. It is also preferable to contain boron, nitrogen, hydrogen, or carbon at this point.

  (B) Step: Next, a mixture is formed on the substrate by using a film forming method in which the first material and the second material are formed in a non-equilibrium state. The film-formed mixture has a columnar member containing the first material and a region formed of the second material and surrounding the columnar member, and the second material is 0.30 ≦ x ≦ 0. .80 in a proportion. When the film forming method is sputtering, it is also preferable to form a film using part of the argon gas as nitrogen or hydrogen gas.

  (C) Step: Next, a columnar member is removed from the mixture to form a porous body. When the mixture is subjected to wet etching using an acid or alkali, the columnar member containing the first material is etched to form a porous body having pores.

  Step (e ′): Next, wet etching using an acid or alkali is performed to widen the pore diameter of the formed porous body.

  Step (d): Furthermore, the porous body having pores with expanded pore diameters is oxidized to obtain an oxide porous body.

  Finally, in order to contain boron, nitrogen, hydrogen, or carbon, ions may be implanted by an ion implantation method, and heat treatment and plasma treatment are preferably performed in nitrogen gas, ammonia gas, or hydrogen gas.

  Further, the steps will be described using (a) to (e) and (e ′).

(A) Step: Prepare a first material (for example, aluminum) and a second material (for example, silicon). The second material and the first material as raw materials are prepared from the first material as shown in FIG. A chip 23 made of the second material is disposed on the target 22.

(B) Step: Formation of Mixture Next, a mixture is formed on the substrate 21. Here, an example in which a sputtering method is used as a film formation method for forming a substance in a non-equilibrium state is shown.

  A mixture is formed on the substrate 21 by magnetron sputtering, which is a film forming method for forming a substance in a non-equilibrium state. The mixture is composed of a columnar member made of a composition containing a first material as a main component and a region containing a second material arranged around it as a main component.

  As a method for forming a film in a non-equilibrium state, a method for forming a mixture using a sputtering method will be described. In addition, 21 is a substrate and 22 is a sputtering target made of the first material. When the sputtering method is used, the ratio between the first material and the second material can be easily changed. A mixture is formed on the substrate 21 by magnetron sputtering, which is a film forming method for forming a substance in a non-equilibrium state. Further, the content of boron, nitrogen, or hydrogen is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995.

The second material and the first material as raw materials are achieved by arranging the chip 23 made of the second material on the target 22 of the first material. In FIG. 2, this chip is divided into a plurality of chips, but of course, the present invention is not limited to this. One chip may be used as long as a desired film can be formed. However, in order to uniformly disperse the uniform columnar members in the region, it is preferable to dispose them on the substrate 21 (for example, on concentric circles). Further, it is preferable that the chip 23 contains boride, nitride, hydride, boron as the carbide, nitrogen, hydrogen, or carbon.
In addition, a fired product obtained by firing a predetermined amount of powder of the first material and the second material can be used as a target material for film formation. It is also preferable to contain boron, nitrogen, hydrogen, or carbon as a compound or mixture in the sintered body.

  Alternatively, a method of separately preparing a target made of the first material and a target made of the second material and simultaneously sputtering both targets 22 may be used.

  The amount of the second material in the formed mixture film is 0.3 ≦ x ≦ 0.8, preferably 0.35 ≦ x ≦ 0.75, and more preferably 0.4 ≦ x ≦ 0. .7. When the amount of the second material is within such a range, a mixture in which columnar members are dispersed in the region is obtained.

  Further, the substrate temperature is 300 ° C. or lower, preferably 200 ° C. or lower.

  When the mixture is formed by such a method, the first material and the second material have a metastable eutectic structure, and the first material has a level of several nanometers in a matrix made of the second material. The nanomaterial (columnar member) is formed, and the first material and the second material are separated in a self-organized manner. The first material at that time has a substantially cylindrical shape, the pore diameter is 1 to 10 nm, and the interval is 3 to 15 nm.

  The amount of the second material in the mixture can be controlled, for example, by changing the amount of the second material tip placed on the first material target.

  When film formation is performed in a non-equilibrium state, particularly in the case of sputtering, the pressure in the reactor when argon gas is flowed is preferably about 0.2 to 1 Pa, or about 0.1 to 1 Pa. The output for forming is preferably about 150 to 1000 W in the case of a 4-inch target. However, the present invention is not particularly limited to this, and any pressure and output may be used as long as argon plasma is stably formed. In particular, film formation by a sputtering method is preferably performed in a state where plasma is not substantially in contact with the deposition target substrate.

  As a substrate, for example, an insulating substrate such as quartz glass or plastic, a semiconductor substrate such as silicon or gallium arsenide, a substrate such as a metal substrate, or one or more films formed on these substrates Is mentioned. Note that the material, thickness, mechanical strength, and the like of the substrate are not particularly limited as long as there is no problem in forming the aluminum silicon mixture.

  Further, the shape of the substrate is not limited to a flat plate shape, but may include a curved surface, a surface having a certain degree of unevenness or a step, etc. Is not to be done.

  A sputtering method is preferable as a film forming method for forming a substance in a non-equilibrium state, but a film forming method for forming a substance in any non-equilibrium state such as resistance heating vapor deposition and electron beam vapor deposition (EB vapor deposition) can be applied. is there.

  In addition, as a method for forming a film, a simultaneous film formation process in which the second material and the first material are formed at the same time may be used, or a stack in which the second material and the first material are stacked in several atomic layers. A film formation process may be used.

  The mixture formed as described above includes a columnar member made of a composition containing the first material as a main component, and a surrounding region containing the second material as a main component.

  The composition of the columnar member is mainly composed of the first material, but may contain other elements such as silicon, oxygen and argon as long as a fine mixture having a columnar structure is obtained. The main component refers to a case where, for example, the ratio of the first material is 80 atomic% or more, or 90 atomic% or more in the component composition ratio of the columnar member portion.

  The composition of the region surrounding the periphery of the columnar member containing the first material is mainly composed of the second material. However, if a fine mixture having a columnar structure is obtained, boron or nitrogen In addition, the content of hydrogen or carbon is preferably y ≧ 0.7, and more preferably 0.8 ≦ y ≦ 0.995. Furthermore, you may contain various elements, such as aluminum, oxygen, and argon. The main component means that the ratio of the second material in the component composition ratio of the region 24 is, for example, 80 atomic% or more, or 90 atomic% or more.

(C) Process: pore formation process The columnar member in said mixture is selectively removed. As this removal method, wet etching using an acid or alkali that selectively dissolves the first material is preferable. As a result, a region having pores mainly remains in the mixture, and a porous body is formed. The pores in the porous body have an interval 2R of 30 nm or less and a pore diameter 2r of 20 nm or less. Preferably, the pore diameter 2r of the pore is 1 to 15 nm, and the center-to-center distance 2R is 5 to 20 nm. It is. The length L is in the range of 1 nm to several μm. Note that the columnar member is selectively removed as long as the substantially columnar portion is removed.

  Examples of the solution used in the wet etching include acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and chromic acid solution that dissolve aluminum as the first material and hardly dissolve silicon as the second material. If there is no problem in pore formation, an alkali such as sodium hydroxide can be used, and it is not particularly limited to the type of acid or the type of alkali. Moreover, you may use what mixed several types of acid solutions or several types of alkali solutions. Etching conditions can be set as appropriate according to the porous body to be produced, for example, solution temperature, concentration, time, and the like.

(D) Oxidation treatment of porous body As an oxidation method of the porous body produced in the step (c), in addition to a method of heating in an oxygen atmosphere, heating in water vapor or air, anodization, oxygen plasma Any oxidation treatment method such as exposure to water is applicable. The second material constituting the porous body is oxidized into an oxide region, and an oxide porous body is obtained. In addition, it is also possible to oxidize simultaneously with process (c) by using an acid or alkali with much moisture. In the present invention, it is mainly described that the porous body is oxidized. However, if necessary, nitriding treatment may be performed instead of the oxidation treatment.

  In addition, as shown in the step (e ′), the present invention expands the pores of the porous body produced in the step (c) and then heats it in an oxygen atmosphere to form the oxide porous body. The method of obtaining may be used. Moreover, when it is not necessary to make all the hole walls into an oxide, the time of the oxidation process may be shortened.

Steps (e) and (e ′): pore diameter expansion step:
As shown in FIG. 5, the step of enlarging the pore diameter performs the step (e) of enlarging the pores of the porous oxide material produced in the step (d). Alternatively, the step of enlarging the pores (e ′) of the porous body produced in the step (c) is performed.

  In order to increase the pore size, the porous body or oxide porous body is immersed in an acid solution (for example, a solution obtained by diluting hydrogen fluoride) or an alkaline solution (such as sodium hydroxide). The pore diameter can be appropriately expanded by pore wide processing (pore diameter expansion processing).

Any acid and alkali may be used for this solution as long as there is no problem in pore enlargement. Moreover, you may use what mixed several types of acid solutions or several types of alkali solutions.
In addition, for pore diameter expansion (pore wide treatment) conditions, for example, solution temperature, concentration, time, and the like can be appropriately set according to the size of the pores to be produced.

  As described above, the method for producing an oxide porous body according to the present invention is a method in which the pore diameter is increased after the porous body is produced, or after the silicon oxide porous body is produced, A method of expanding the pore size is included.

  Finally, in order to contain boron, nitrogen, hydrogen, or carbon, ions may be implanted by an ion implantation method, and heat treatment and plasma treatment are preferably performed in nitrogen gas, ammonia gas, or hydrogen gas.

(Embodiment 20: Method for producing porous silicon oxide)
The present embodiment is applied to the method for manufacturing a silicon oxide porous body according to the sixteenth embodiment described above.

  The method for producing a silicon oxide porous body containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a mixture including aluminum and silicon, and includes a columnar member including aluminum. A step of preparing an aluminum silicon mixture containing silicon in a ratio of 0.3 ≦ x ≦ 0.8, and a columnar shape containing the aluminum from the aluminum silicon mixture. It is characterized by having a removing step of removing the member, and a step of oxidizing the aluminum silicon mixture after or simultaneously with the removing step.

  The silicon oxide porous body manufacturing method includes: (a) a step of preparing aluminum and silicon; and (b) a columnar shape containing aluminum using a film forming method of forming a material in a non-equilibrium state between the aluminum and silicon. A silicon region surrounding the columnar member, and forming an aluminum silicon mixture containing silicon in a ratio of 0.3 ≦ x ≦ 0.8, (c) of the aluminum silicon mixture It is preferable to include a step of etching aluminum to form a porous silicon body having pores, and (d) a step of oxidizing the porous silicon body having pores.

  The silicon oxide porous body manufacturing method includes: (a) a step of preparing aluminum and silicon; and (b) a columnar shape containing aluminum using a film forming method of forming a material in a non-equilibrium state between the aluminum and silicon. A silicon region surrounding the columnar member, and forming an aluminum silicon mixture containing silicon in a ratio of 0.3 ≦ x ≦ 0.8, (c) of the aluminum silicon mixture Etching aluminum to form a porous silicon body having pores, (d) oxidizing the porous silicon body having pores, and (e) expanding the pore diameter. preferable.

  The silicon oxide porous body manufacturing method includes: (a) a step of preparing aluminum and silicon; and (b) a columnar shape containing aluminum using a film forming method of forming a material in a non-equilibrium state between the aluminum and silicon. A silicon region surrounding the columnar member, and forming an aluminum silicon mixture containing silicon in a ratio of 0.3 ≦ x ≦ 0.8, (c) of the aluminum silicon mixture Etching the aluminum to form a porous silicon body having pores; (e ′) expanding the pore diameter of the porous silicon body; and (d) oxidizing the porous silicon body having pores. It is preferable to have the process of doing.

  The step of expanding the pores is preferably wet etching using acid or alkali.

  The oxidation step is preferably thermal oxidation or oxidation using an aqueous solution. The film forming method for forming the substance in the non-equilibrium state is preferably a sputtering method.

  Finally, in order to contain boron, nitrogen, hydrogen, or carbon, ions may be implanted by an ion implantation method, and heat treatment and plasma treatment are preferably performed in nitrogen gas, ammonia gas, or hydrogen gas.

(Embodiment 21: Method for producing germanium oxide porous body)
The present embodiment is applied to the method for manufacturing a germanium oxide porous body according to the seventeenth embodiment described above.

  A method for producing a porous germanium oxide containing boron, nitrogen, hydrogen, or carbon according to this embodiment is a mixture including aluminum and germanium, and includes a columnar member including aluminum. A step of preparing an aluminum germanium mixture having a germanium region surrounding the columnar member and containing germanium in a ratio of 0.3 ≦ x ≦ 0.8 with respect to the total amount of aluminum and germanium, the aluminum germanium mixture It has the removal process which removes the columnar member containing this aluminum from a body, and the process which oxidizes this aluminum germanium mixture simultaneously with or after this removal process.

  The method for producing a porous germanium oxide includes: (a) a step of preparing aluminum and germanium; and (b) a columnar shape containing aluminum using a film forming method of forming a material in a non-equilibrium state of the aluminum and germanium. And (c) forming an aluminum germanium mixture containing germanium in a ratio of 0.3 ≦ x ≦ 0.8, and a germanium region surrounding the columnar member. It is preferable to have a step of etching aluminum to form a porous germanium body having pores, and (d) a step of oxidizing the porous germanium body having pores.

  The method for producing a porous germanium oxide includes: (a) a step of preparing aluminum and germanium; and (b) a columnar shape containing aluminum using a film forming method of forming a material in a non-equilibrium state of the aluminum and germanium. And (c) forming an aluminum germanium mixture containing germanium in a ratio of 0.3 ≦ x ≦ 0.8, and a germanium region surrounding the columnar member. Etching aluminum to form a porous germanium porous body, (d) oxidizing the porous porous germanium body, and (e) expanding the pore diameter. preferable.

  The method for producing a porous germanium oxide includes: (a) a step of preparing aluminum and germanium; and (b) a columnar shape containing aluminum using a film forming method of forming a material in a non-equilibrium state of the aluminum and germanium. And (c) forming an aluminum germanium mixture containing germanium in a ratio of 0.3 ≦ x ≦ 0.8, and a germanium region surrounding the columnar member. Etching aluminum to form a porous germanium porous body; (e ′) expanding the pore diameter of the porous germanium porous body; and (d) oxidizing the porous germanium porous body. It is preferable to have the process of doing.

  The step of expanding the pores is preferably wet etching using acid or alkali.

The oxidation step is preferably thermal oxidation or oxidation using an aqueous solution. The film forming method for forming the substance in the non-equilibrium state is preferably a sputtering method.
Finally, in order to contain boron, nitrogen, hydrogen, or carbon, ions may be implanted by an ion implantation method, and heat treatment and plasma treatment are preferably performed in nitrogen gas, ammonia gas, or hydrogen gas.

(Embodiment 22: Method for producing porous silicon germanium oxide)
This embodiment is applied to the method for producing a porous silicon germanium oxide body according to Embodiment 18 described above.

  A method for producing a porous silicon germanium oxide containing boron, nitrogen, hydrogen, or carbon according to the present embodiment is a mixture including aluminum and silicon germanium, and includes a columnar shape including aluminum. A step of preparing an aluminum silicon germanium mixture having a member and a silicon germanium region surrounding the columnar member and containing a total amount of silicon and germanium in a ratio of 0.3 ≦ x ≦ 0.8; It is characterized by having a removing step of removing the columnar member containing aluminum from the germanium mixture, and a step of oxidizing the aluminum silicon germanium mixture simultaneously with or after the removing step.

  The method for producing a porous silicon germanium oxide includes: (a) a step of preparing aluminum, silicon, and germanium; (b) a film forming method of forming a material in a non-equilibrium state of the aluminum, silicon, and germanium. And an aluminum silicon germanium mixture having a columnar member containing aluminum and a silicon germanium region surrounding the columnar member and containing the total amount of silicon and germanium in a ratio of 0.3 ≦ x ≦ 0.8. (C) etching the aluminum of the aluminum silicon germanium mixture to form a silicon germanium porous body having pores; and (d) oxidizing the silicon germanium porous body having pores. Is preferred.

  The method for producing a porous silicon germanium oxide includes: (a) a step of preparing aluminum, silicon, and germanium; (b) a film forming method of forming a material in a non-equilibrium state of the aluminum, silicon, and germanium. And an aluminum silicon germanium mixture having a columnar member containing aluminum and a silicon germanium region surrounding the columnar member and containing the total amount of silicon and germanium in a ratio of 0.3 ≦ x ≦ 0.8. (C) etching the aluminum of the aluminum silicon germanium mixture to form a silicon germanium porous body having pores; (d) oxidizing the silicon germanium porous body having pores; e) It is preferable to have a step of expanding the pore diameter.

  The method for producing a porous silicon germanium oxide includes: (a) a step of preparing aluminum, silicon, and germanium; (b) a film forming method of forming a material in a non-equilibrium state of the aluminum, silicon, and germanium. And an aluminum silicon germanium mixture having a columnar member containing aluminum and a silicon germanium region surrounding the columnar member and containing the total amount of silicon and germanium in a ratio of 0.3 ≦ x ≦ 0.8. (C) etching the aluminum of the aluminum silicon germanium mixture to form a silicon germanium porous body having pores; (e ′) expanding the pore diameter of the pores of the silicon germanium porous body; (D) having a step of oxidizing the silicon germanium nanomixture having the pores; It is preferable to do this.

  The step of expanding the pores is preferably wet etching using acid or alkali.

  The oxidizing step is preferably thermal oxidation or oxidation in an aqueous solution.

  The film forming method for forming the substance in the non-equilibrium state is preferably a sputtering method.

  Finally, in order to contain boron, nitrogen, hydrogen, or carbon, ions may be implanted by an ion implantation method, and heat treatment and plasma treatment are preferably performed in nitrogen gas, ammonia gas, or hydrogen gas.

(Embodiment 23: Other manufacturing method for producing oxide porous body)
The present embodiment is applied to another method for manufacturing the porous oxide body of the fifteenth embodiment. In order to obtain an oxide porous body containing boron, nitrogen, hydrogen, or carbon, not only the above-described method, but also anodizing the mixture, the porous formation and the oxidation treatment are substantially performed. Can be done simultaneously.

  FIG. 7 is a schematic view showing an example of an anodizing apparatus used in the present embodiment. In FIG. 7, 70 is a mixture (for example, a mixture having aluminum as a first material constituting a columnar member and silicon as a region surrounding the periphery), 71 is a thermostat, 72 is a cathode of a Pt plate, 73 is an electrolytic solution, 74 is a reaction vessel, 75 is a power source for applying an anodizing voltage, and 76 is an ammeter for measuring an anodizing current. Although omitted in the figure, a computer that automatically controls and measures voltage and current is also incorporated.

  The mixture 70 and the cathode 72 are arranged in an electrolytic solution 73 maintained at a constant temperature by a thermostatic chamber 71, and anodization is performed by applying a voltage between the aluminum silicon mixed film and the cathode 72 from a power source 75. .

  Examples of the electrolytic solution used for anodization include oxalic acid, phosphoric acid, sulfuric acid, nitric acid, and chromic acid solution, but are not particularly limited as long as there is no problem in pore formation by anodization. Various conditions such as an anodic oxidation voltage and temperature according to each electrolytic solution can be appropriately set according to the oxide nanomixture to be produced.

  By anodization, aluminum is removed from the mixture to form pores, and at the same time, silicon in the silicon region is oxidized to form a silicon oxide region. As a result, a silicon oxide region having pores remains in the mixture, and a silicon oxide porous body is formed. In addition, as for the space | interval and diameter of a pore of a silicon oxide porous body, the space | interval 2R is 15 nm or less, and the hole diameter 2r is 10 nm or less, for example. The pore diameter 2r of the pores can be 1 to 9 nm and the center distance 2R can be 3 to 10 nm. The length L is in the range of 2 nm to several μm.

After the anodizing step, a step of expanding the pore size of the porous layer may be performed.
For example, the pore size can be appropriately expanded by pore wide treatment (pore size expansion treatment) immersed in an acid solution that dissolves silicon (for example, a solution in which hydrogen fluoride is diluted) or an alkaline solution (such as sodium hydroxide). .

  Any acid and alkali may be used for this solution as long as there is no problem in enlargement of pores. Also, a mixture of several types of acid solutions or several types of alkali solutions may be used.

In addition, for pore diameter expansion (pore wide treatment) conditions, for example, solution temperature, concentration, time, and the like can be appropriately set according to the size of the pores to be produced.

Hereinafter, the present invention will be described with reference to examples.

  In the following examples, the first material and the second material are characterized by containing boron, nitrogen, hydrogen, and carbon as the third material. When the material is A, the second material is B, and the third material is C, x and y included in the following equation are used to express the composition of the material.

(A _x B _1-x ) _y C _1-y
Here, x and y can take values between 0 and 1, and can be converted to atomic% by multiplying by 100. Hereinafter, this notation is applied to the composition of the material.

  This example relates to formation of a mixture containing boron, nitrogen, hydrogen, or carbon, and selecting aluminum as the first material and silicon as the second material.

  A sputtering method is selected as a non-equilibrium film formation method, and an example in which an aluminum silicon mixture in which an average interval 2R of columnar aluminum is 8 nm, an average diameter 2r is 5 nm, and a length L is 50 nm is shown. For example, the target composition satisfies x = 0.53 and y = 0.97.

  As shown in FIG. 2, a circular sputtering target having a diameter of 4 inches (101.6 mm) is obtained by sintering aluminum, silicon, and boron so that x = 0.53 and y = 0.97. Got ready. Sputtering conditions were as follows: RF flow rate, Ar flow rate: 25 sccm, discharge pressure: 0.1 Pa, input power: 120 W. The substrate temperature was room temperature (25 ° C.).

  Note that although a sintered body of three elements is used here as a target, a divided target may be used. In addition, it is also preferable to set the composition to a target value by disposing a chip on the target. In particular, a silicon chip, silicon boride, silicon nitride, silicon hydride, or silicon carbide may be disposed on the aluminum target. Other compounds on the aluminum side may also be used.

  After film formation, the mixture was observed with an FE-SEM (field emission scanning electron microscope). As shown in FIG. 4A, the shape of the surface seen from the diagonally upward direction of the substrate is a columnar member (first member) containing circular aluminum surrounded by a silicon region (region 42 mainly composed of the second material). The region 41) mainly composed of the above material was two-dimensionally arranged. The hole diameter of the columnar member portion containing aluminum was 5 nm, and the average center distance was 8 nm. Moreover, when the cross section was observed with FE-SEM, the length was 50 nm and the columnar members containing each aluminum were mutually independent.

  Boron was also detected from elemental analysis and had a composition of approximately y = 0.97. However, since the structure of the mixture was fine, it was not clear whether it was contained only on one side or both sides of aluminum and silicon. However, the crystallization of aluminum has progressed and the tendency of silicon to become amorphous has been found by observation with a transmission electron microscope (TEM), and boron can easily bond to dangling bonds of amorphous silicon. It is speculated that there is.

Next, in the same sputtering method, a film was formed under the above conditions by using a target made of aluminum, silicon, and nitrogen that was sintered so that x = 0.53 and y = 0.97.
Concerning the inclusion of nitrogen and hydrogen, even if it is not contained in the target, it can be contained in the deposited film by using part of the argon of the sputtering gas as nitrogen or hydrogen.

  As shown in FIG. 4 (a), the surface shape of the film viewed from the obliquely upward direction of the substrate by an FE-SEM (field emission scanning electron microscope) after film formation is a columnar member including circular aluminum surrounded by a silicon region. Were arranged two-dimensionally. The hole diameter of the columnar member portion containing aluminum was 5 nm, and the average center distance was 8 nm. Moreover, when the cross section was observed with FE-SEM, the length was 50 nm and the columnar members containing each aluminum were mutually independent. Nitrogen was also detected from elemental analysis and had a composition of approximately y = 0.97.

  However, since the structure of the mixture was fine, it was not clear whether it was contained only on one side or both sides of aluminum and silicon. However, the crystallization of aluminum has progressed and the tendency of silicon to become amorphous has been found by observation with a transmission electron microscope (TEM), and nitrogen can easily bond to dangling bonds of amorphous silicon. It is speculated that there is.

Next, in the same sputtering method, a film was formed under the above conditions using a target made of aluminum, silicon, and hydrogen so that x = 0.53 and y = 0.97.
As shown in FIG. 4 (a), the surface shape of the film viewed from the obliquely upward direction of the substrate by an FE-SEM (field emission scanning electron microscope) after film formation is a columnar member including circular aluminum surrounded by a silicon region. Were arranged two-dimensionally.

  The hole diameter of the columnar member portion containing aluminum was 5 nm, and the average center distance was 8 nm. Moreover, when the cross section was observed with FE-SEM, the length was 50 nm and the columnar members containing each aluminum were mutually independent. Hydrogen was also detected from elemental analysis and had a composition of approximately y = 0.97.

  However, since the structure of the mixture was fine, it was not clear whether it was contained only on one side or both sides of aluminum and silicon. However, the crystallization of aluminum has progressed and the tendency of silicon to become amorphous has been found by observation with a transmission electron microscope (TEM), and hydrogen can easily bond to dangling bonds of amorphous silicon. It is speculated that there is. However, the possibility that hydrogen is located between the lattices of aluminum and silicon is not excluded.

  Furthermore, when hydrogen was used as the sputtering gas, the content of hydrogen was found and the composition was y = 0.7. Therefore, it can be seen that the content of about 30 atomic% is also possible.

Next, in the same sputtering method, a film was formed under the above conditions using a target made of aluminum, silicon, and carbon sintered so that x = 0.53 and y = 0.97.
As shown in FIG. 4 (a), the surface shape of the film viewed from the obliquely upward direction of the substrate by an FE-SEM (field emission scanning electron microscope) after film formation is a columnar member including circular aluminum surrounded by a silicon region. Were arranged two-dimensionally.

  The hole diameter of the columnar member portion containing aluminum was 5 nm, and the average center distance was 8 nm. Moreover, when the cross section was observed with FE-SEM, the length was 50 nm and the columnar members containing each aluminum were mutually independent. Carbon was also detected from elemental analysis and had a composition of approximately y = 0.97.

  However, since the structure of the mixture was fine, it was not clear whether it was contained only on one side or both sides of aluminum and silicon. However, the crystallization of aluminum has progressed and the tendency of silicon to become amorphous has been found by observation with a transmission electron microscope (TEM), and carbon can easily bond to dangling bonds of amorphous silicon. It is speculated that there is.

  The above shows that an aluminum-silicon mixture containing boron, nitrogen, hydrogen, or carbon has a structure in which columnar members including circular aluminum surrounded by a silicon region are two-dimensionally arranged. Yes. Moreover, when hydrogen is taken as an example, it also shows that 30 atomic% is contained.

  This example forms a porous body from a mixture obtained when boron, nitrogen, hydrogen, or carbon is contained, and aluminum is selected as the first material and silicon is selected as the second material. It is about.

  Each of the boron, nitrogen, hydrogen, or carbon-containing mixtures obtained in Example 1 is immersed in 98% concentrated sulfuric acid in an almost anhydrous state. Then, regardless of the content of boron, nitrogen, hydrogen, and carbon, only the columnar aluminum portion is dissolved, the portion becomes a cavity, the pore diameter is 5 nm, and the average center-to-center spacing is 8 nm. Confirmed with SEM.

  Further, after the cylindrical aluminum is removed from the elemental analysis, silicon and boron, nitrogen, hydrogen, or carbon are detected from each mixture, and aluminum is also detected. In order to dissolve the columnar aluminum, it is not limited to concentrated sulfuric acid if a material that dissolves only aluminum without dissolving silicon or a material whose relative dissolution rate differs greatly is selected.

In this case, since the silicon contains a large number of dangling bonds, the surface is particularly easily oxidized, and it is not denied that some etching involves oxidation.
The above shows that a porous body containing boron, nitrogen, hydrogen, or carbon can be easily obtained by etching the mixture.

Example 3 is a comparative example.
This example relates to forming an oxide body from a mixture containing boron, nitrogen, hydrogen, or carbon, and selecting aluminum as the first material and silicon as the second material. Is.

  The mixture containing boron, nitrogen, hydrogen, or carbon obtained in Example 1 is immersed in 5 wt% phosphoric acid. Then, it is confirmed by FE-SEM that only the cylindrical aluminum portion is dissolved and the portion becomes a cavity regardless of the contents of boron, nitrogen, hydrogen, and carbon.

  Further, they are placed in a heat treatment furnace into which oxygen can be introduced, and heated at 600 ° C. for 2 hours in an oxygen atmosphere. As a result, not only oxygen but also silicon and boron, nitrogen, hydrogen, or carbon are detected from the respective mixtures from elemental analysis, and aluminum is also detected. When observed again with FE-SEM, the hole diameter was 5 nm and the average center-to-center spacing was 8 nm, as before heat treatment.

  In order to dissolve the columnar aluminum, it is not limited to phosphoric acid if a material that dissolves only aluminum without dissolving silicon or a material whose relative dissolution rate is different is selected.

  The above shows that an oxide porous body containing boron, nitrogen, hydrogen, or carbon can be easily obtained by etching the mixture and heat treatment in an oxygen atmosphere.

  This embodiment relates to a method for mixing boron, nitrogen, hydrogen, and carbon into a mixture.

  In the method of Example 1, it was shown that the method of containing boron, nitrogen, hydrogen, and carbon in the mixture was achieved by using a sputtering target mixed and sintered with aluminum and silicon.

  Other methods will be described below.

  (1) First, it is shown that the compound can be arranged on the target. In particular, boron is taken as an example. First, two SiB6 5 mm square chips were placed on a target made of 4 inch aluminum and silicon. At this time, the composition of aluminum and silicon is x = 0.53. When these films are formed under the same sputtering conditions as in Example 1, the composition of the obtained film is confirmed to contain boron from elemental analysis, and approximately y = 0.97.

  (2) Next, a case in which a hydrogen gas mixed with an argon gas is used as a sputtering gas will be described. The mixing ratio of argon and hydrogen was 30% hydrogen in terms of flow rate. The sputtering conditions at this time were Ar2 / H2 flow rate: 25 sccm in total, discharge pressure: 0.1 Pa, and input power: 120 W. The substrate temperature is room temperature (25 ° C.). A target made of aluminum and silicon satisfying x = 0.53 is used. When the composition of the film after film formation is analyzed, the amount of hydrogen mixed in is approximately y = 0.7.

  From the above, it has been shown that even if not all the raw materials are mixed in the target, the method of chip arrangement, the method of mixing from the sputtering gas, and the like are effective means.

  The present example relates to a method for mixing boron, nitrogen, hydrogen, and carbon into a porous body produced from a mixture. In particular, the present invention relates to a method other than the means for using the mixture prepared in Example 4 and processing it to form a porous body.

  Up to Example 4, boron, nitrogen, hydrogen, or carbon is mixed before formation of the mixture, but other means that can be mixed after formation of the porous body will be described.

(1) First, a porous body is prepared from a mixture containing no boron, nitrogen, hydrogen, or carbon by the same means as in Example 2. Further, as an example, boron is ionized by the ion implantation method and implanted into the porous body. As a result, ionized boron is contained in the amorphous silicon portion that forms the porosity. In this case, no doping is performed at a concentration satisfying y = 0.97, and a so-called doping concentration of about 10 ²⁰ cm ⁻¹ is possible. Therefore, boron is added at a concentration sufficiently lower than y = 0.0.99. In this case, it is effective for the purpose of controlling the conductivity of silicon.

  (2) Next, a porous body is prepared from a mixture containing no boron, nitrogen, hydrogen, or carbon by the same means as in Example 2. Further, nitrogen plasma or nitrogen radical irradiation is performed while heating the porous body to 600 ° C. in a container capable of heating the porous body to promote nitriding. Thereafter, compositional analysis of nitrogen in the film shows y = 0.90. This means can be applied not only to nitrogen but also to hydrogen.

  (3) Next, a porous body is prepared from a mixture containing no boron, nitrogen, hydrogen, or carbon by the same means as in Example 2. Further, the porous body is placed in a furnace that can be heated by introducing gas, and an ammonia gas is flowed at 10 sccm to perform a heat treatment at 600 ° C. Then, a part of the silicon portion is nitrided. The composition at that time is approximately y = 0.90.

  This example relates to a method of mixing boron, nitrogen, hydrogen, and carbon into an oxide porous body produced from a mixture. In particular, the present invention relates to a method other than the means for using the mixture produced in Example 4 or the porous body produced in Example 5 and processing it to form an oxide porous body.

(1) First, an oxide porous body is prepared from a mixture containing no boron, nitrogen, hydrogen, or carbon by the same means as in Example 3. Further, as an example, boron is ionized by the ion implantation method and implanted into the porous oxide material. As a result, ionized boron is contained in the silicon oxide portion forming the oxide porous. In this case, no doping is performed at a concentration satisfying y = 0.97, and a so-called doping concentration of about 10 ²⁰ cm ⁻¹ is possible. Therefore, boron is added at a concentration sufficiently lower than y = 0.0.99. In this case, it is effective for the purpose of controlling the conductivity of silicon.

  (2) Next, an oxide porous body is prepared from a mixture containing no boron, nitrogen, hydrogen, or carbon by the same means as in Example 3. Furthermore, nitrogen plasma or nitrogen radical irradiation is performed while heating at 600 ° C. in a container capable of heating the oxide porous body to promote nitriding. Thereafter, the compositional analysis of nitrogen in the film shows y = 0.97. This means can be applied not only to nitrogen but also to hydrogen.

  (3) Next, an oxide porous body is prepared from a mixture containing no boron, nitrogen, hydrogen, or carbon by the same means as in Example 2. Further, the porous oxide body is placed in a furnace that can be heated by introducing gas, and ammonia gas is flowed at 10 sccm to perform a heat treatment at 600 ° C. Then, a part of the silicon portion is nitrided. The composition at that time is approximately y = 0.97.

  This example relates to a change in film strength due to mixing of boron, nitrogen, hydrogen, and carbon into a mixture.

  The film strength means resistance to acid or alkali and mechanical strength. Moreover, since it is estimated that the property of a porous body and an oxide porous body is especially the same regarding acid resistance and alkali resistance, it implements using a mixture as an example.

  (1) First, the same aluminum silicon mixture containing boron, nitrogen, hydrogen, and carbon as in Example 1 and an aluminum silicon mixture not containing them were prepared, and these were mixed with sodium hydroxide 1M at room temperature (24 degrees). The film is immersed in an aqueous solution, and the dissolution characteristics of the film are observed from the dissolution state of the structure. In particular, a hydrogen-containing material is 30 atomic%.

  Observation of dissolution of the mixture containing no boron, nitrogen, hydrogen, or carbon reveals that after 1 minute, the aluminum portion is dissolved, the silicon portion is broken, and the fine structure is broken. However, the mixture containing boron, nitrogen, hydrogen, and carbon naturally dissolves the aluminum portion but not the silicon portion. Further, even after 3 minutes, there is no significant change in the shape of the silicon portion, indicating that the resistance to alkali is improved. This result is applied not only to the mixture but also to the porous body and the oxide porous body.

  (2) Next, as an index indicating the hardness of the above four types of films, a comparison is made by the amount of abrasion due to polishing. The film was affixed to a polishing jig and slid at a radius of 100 mmφ on the rotating pad of the polishing apparatus, and the amount of polishing with a 1/4 μm diamond slurry was measured. When the polishing amount of a mixture containing no boron, nitrogen, or hydrogen is 1, and the polishing amount of a mixture containing other boron, nitrogen, hydrogen, and carbon is compared, boron, nitrogen, and carbon are tightly around 0.7. Met. Moreover, the thing containing hydrogen was around 0.9.

  As described above, it can be confirmed that the hardness of the film is increased by containing boron, nitrogen and boron.

  As described above, the present invention relates to an electronic device using a quantum effect such as a quantum dot, a quantum wire, a quantum wire transistor, a single electron transistor, or a single electron memory, a magnetic device in which a porous material is filled with a magnetic material, The present invention can be applied to the use of magnetic recording media and electronic equipment such as an information processing apparatus equipped with these electronic / magnetic devices.

It is a schematic diagram which shows embodiment of the mixture to which the structure by this invention is applied, (a) is a top view, (b) is sectional drawing along the A-A 'line in (a). It is a schematic diagram which shows embodiment of the manufacturing method of the structure by this invention using sputtering method. It is a schematic diagram which shows embodiment of the porous body to which the structure by this invention is applied, (a) is a top view, (b) is sectional drawing along the B-B 'line in (a). (A)-(c) is a figure which shows the preparation methods of the porous body to which the structure by this invention is applied. It is a schematic diagram which shows embodiment of the oxide porous body to which the structure by this invention is applied, (a) is a top view, (b) is sectional drawing along CC 'line in (a). . (A)-(d) is a figure which shows an example of the preparation methods of the oxide porous body to which the structure by this invention is applied. It is a figure which shows the structural example of the anodizing apparatus used with the manufacturing method of the oxide porous body to which the structure by this invention is applied. It is a figure which shows an example of the anodic oxidation alumina whose pore space | interval of a conventional example is 10 nm or less. It is a figure which shows an example of the porous silicon which anodized the silicon of the prior art example.

Explanation of symbols

11 Region mainly composed of the first material (first member, columnar structure)
12 Region mainly composed of second material (second member, silicon germanium region)
13 Substrate 14 Mixture (Structure)
21 Substrate 22 Target 23 Chip 31 Pore 32 Region 33 Substrate 34 Porous Body (Structure)
41 Region mainly composed of first material (first member, columnar structure)
42 Region mainly composed of second material (second member, silicon germanium region)
43 mixture 44 substrate 45 porous body (structure)
46 pore 47 enlarged pore 51 pore 52 oxide region (second member)
53 Substrate 54 Oxide porous body (structure)
61 Region 62 based on first material 62 Substrate 63 Mixture 64 Region 65 based on second material 65 Porous body 66 Pore 67 Expanded pore 68 Oxide porous body (structure)
70 Mixture 71 Constant temperature bath 72 Pt cathode 73 Electrolyte 74 Reaction vessel 75 Power source 76 Ammeter 81 Independent pore 82 Independent pore 83 Anodized alumina 84 Substrate 85 Barrier layer 91 Pore 92 Silicon

Claims (4)

In a structure composed of a columnar first member and a second member surrounding the first member, the structure contains at least one component of boron, nitrogen, hydrogen, and carbon,
The first member contains aluminum;
The second member is silicon, or silicon and germanium ;
The structure according to claim 1, wherein a ratio of at least one of boron, nitrogen, hydrogen, and carbon is 30 atomic% or less with respect to a total of the first member and the second member .   The structure according to claim 1, wherein the first member has a diameter of 50 nm or less. The structure according to claim 1 or 2 , wherein the first member has a center interval of 30 nm or less. Structure having a hole formed by removing the first member from the structure according to any one of claims 1 to 3.

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