Film manufacturing method, lamination structure and bolometer

Abstract

To provide a film manufacturing method in which a degree of orientation is easily controlled, a lamination structure and a bolometer.SOLUTION: A film manufacturing method includes the steps of: forming an initial self-organization film on a base material; primarily drying the formed initial self-organization film; forming a self-organization film by dipping the primarily dried initial self-organization film in a solution in which a silane coupling agent is dissolved; secondarily drying the formed self-organization film; and laminating a nano carbon layer on the secondarily dried self-organization film.SELECTED DRAWING: Figure 14

Description

Technical Field

[0001] The present disclosure relates to a film manufacturing method, a laminated structure, and a bolometer.

Background Art

[0002] It is known to use carbon nanotubes in electric devices.

[0003] For example, Patent Document 1 discloses a carbon nanotube FET (FIELD EFFECT TRANSISTOR) using carbon nanotubes.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The carbon nanotube FET disclosed in Patent Document 1 treats the substrate surface with aminosilane to fix the carbon nanotubes and introduces amino groups onto the substrate surface. The film of carbon nanotubes formed using the amino groups tends to have a local orientation, and it is difficult to control the degree of orientation of the carbon nanotubes.

[0006] An object of the present disclosure is to provide a film manufacturing method, a laminated structure, and a bolometer that solve the above-described problems.

Means for Solving the Problems

[0007] The method for manufacturing a film according to the present disclosure includes the steps of forming an initial self-assembled film on a substrate, primary drying the formed initial self-assembled film, immersing the primarily dried initial self-assembled film in a solution in which a silane coupling agent is dissolved to form a self-assembled film, secondary drying the formed self-assembled film, and laminating a nanocarbon layer on the secondarily dried self-assembled film.

[0008] The laminated structure according to the present disclosure sequentially includes a substrate, a self-assembled film, and a nanocarbon layer having an orientation parameter, wherein the orientation parameter has an orientation component and a random component, and the orientation component is an attenuation constant λ related to the local degree of orientation c with the side length d of one side of the square observation region of the nanocarbon layer and a constant value S full and is represented by Equation (3) which is a function of, and the attenuation constant λ c is 300 nm or more. Laminated structure.

Number

Advantages of the Invention

[0009] According to the film manufacturing method, laminated structure, and bolometer according to the present disclosure, the degree of orientation can be easily controlled.

Brief Description of the Drawings

[0010]

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Mode for Carrying Out the Invention

[0011] Hereinafter, each embodiment according to the present disclosure will be described with reference to the drawings. Note that the drawings and the specific configurations used in each embodiment shall not be used for interpreting the disclosure. The same or corresponding configurations in all the drawings are denoted by the same reference numerals, and common descriptions are omitted. Note that in the present disclosure, the drawings are associated with one or more embodiments.

[0012] Hereinafter, an example of the configuration of the stacked structure according to the present disclosure will be described with reference to FIGS. 1 to 11.

[0013] (Configuration of the stacked structure) For example, the stacked structure 11 is included in elements such as a bolometer and a thin film transistor. As shown in FIG. 1, the stacked structure 11 sequentially includes a substrate 111, a self-assembled film 112A, and a nanocarbon layer 113. For example, the stacked structure 11 may include the self-assembled film 112A on the stacked surface 111L of the substrate 111. For example, the substrate 111 is a Si substrate processed using a silicon wafer. For example, the substrate 111 may be a monomer such as parylene (registered trademark), a resin such as polyimide, or an organic material such as plastic. For example, a readout circuit may be formed on the substrate 111. For example, the substrate 111 may have a base insulating layer 111X that is electrically insulating. As methods for forming the base insulating layer 111X, there are a method of subjecting the substrate 111 to heat treatment and a method of directly forming the base insulating layer 111X by CVD (Chemical Vapor Deposition). The base insulating layer 111X is, for example, silicon oxide, silicon nitride, or the like. For example, in the present disclosure, the substrate 111 is a Si substrate having a base insulating layer 111X. Also, in the present disclosure, the base insulating layer 111X is silicon oxide.

[0014] (Self-assembled film) The self-assembled film 112A contains a silane coupling agent 22 for forming a nanocarbon layer 113 on the substrate 111. For example, an operator may use a silane coupling agent 22 having an amino group in order to improve the adhesion of the CNT42 described later. Examples of the silane coupling agent 22 include 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane, 3-aminopropylmethyltriethoxysilane, 3-aminopropylmethyltrimethoxysilane, and the like. The amount of the self-assembled film 112A is controlled by adjusting the concentration of the dissolution solution 2β described later. Thereby, the local orientation degree of the nanocarbon contained in the nanocarbon layer 113 is suppressed. The orientation degree represents the degree of orientation of the nanocarbon.

[0015] (Nanocarbon layer) The nanocarbon layer 113 is laminated on the substrate 111 via the self-assembled film 112A. For example, the nanocarbon layer 113 can act as a light receiving part for infrared rays. The nanocarbon layer 113 contains nanocarbon. For example, the nanocarbon forms a network within the nanocarbon layer 113. Nanocarbon refers to nano-sized carbon materials mainly composed of carbon, such as carbon nanotubes (Curbon nano tube: CNT), carbon nanohorns (Curbon Nanohorn: CNH), CNHs (Curbon Nanohorns: CNHs) formed by the aggregation of carbon nanohorns, carbon nano brushes (Curbon nano brush: CNB), carbon nanotwists, graphene, fullerenes, etc. For example, in the present disclosure, the nanocarbon layer 113 contains CNTs 42. In the present disclosure, the nanocarbon layer 113 has a CNT network in which each CNT 42 is randomly oriented to form a network with each other. The CNT 42 is a fibrous material with a diameter of 0.6 to 1.5 nm and a length of 100 nm to 5.0 μm for each. The properties of the CNT 42 change depending on the arrangement of the six-membered rings in the circumferential direction. In the CNT 42, a cylindrical CNT made of a single graphene sheet is called a single-layer CNT, and a multi-layer CNT is called a multi-layer CNT in which a plurality of CNTs with different diameters are coaxially overlapped to form a plurality of layers. A two-layer formed one is called a two-layer CNT. For example, the CNT 42 may be any of a single-layer CNT, a two-layer CNT, and a multi-layer CNT. For example, the CNT 42 in the present disclosure is a single-layer CNT. There are semiconductor-type CNTs showing semiconductor properties and metallic-type CNTs showing metallic properties. A single-layer CNT usually contains semiconductor-type CNTs and metallic-type CNTs in a ratio of 2:1. Therefore, a separation process is required when using a large amount of CNTs showing one property. For example, in the nanocarbon layer 113, semiconductor-type CNTs and metallic-type CNTs may coexist in a mixed state. In the plurality of CNTs 42, there are mixed semi-conductive CNTs and metallic CNTs respectively. For example, for CNT 42, a step of separating semi-conductive CNTs from the plurality of CNTs 42 may be performed, and the semi-conductive CNTs may be contained in an amount of 90% or more of the whole. For example, for CNT 42, after the separation step, the semi-conductive CNTs may be contained in an amount of 92% or more of the whole. For example, for CNT 42, the semi-conductive CNTs may be contained in an amount of 94% or more of the whole. For example, for CNT 42, after the separation step, the semi-conductive CNTs may be contained in an amount of 96% or more of the whole. For example, for CNT 42, after the separation step, the semi-conductive CNTs may be contained in an amount of 98% or more of the whole. the attenuation constant λ described later c is related to the local orientation degree of the nanocarbon layer 113. For example, the attenuation constant λ c can be used as an index representing the orientation degree of the CNT network formed by the CNTs 42 contained in the nanocarbon layer 113. Among the orientation component and the random component that the orientation parameter described later has, the orientation component is the attenuation constant λ c and the side length d of one side of the square observation region of the nanocarbon layer, and a constant value S full and is represented by Equation (3) which is a function of them.

Equation

[0016] (Index of orientation degree: attenuation constant) The orientation degree of the nanocarbon layer 113 is confirmed as follows. In the present disclosure, the orientation angle of the oriented object is calculated for each one in pixel units, and the orientation degree is evaluated by the orientation parameter S 2D (d) (Equation (1)) representing the orientation order in the square observation region. The orientation parameter S 2D (d) (Equation (1)) is a quantity that takes a value from 0 to 1. In the following description, the oriented material refers to CNT42.

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[0017] (Image processing for determining the attenuation constant) As a whole process, the operator obtains the orientation component from the captured image obtained from the imaging device, repeats these processes in each observation region, and then determines the attenuation constant λ from each orientation component c to evaluate the degree of orientation of the nanocarbon layer 113.

[0018] For example, the imaging device may include an atomic force microscope (AFM), a scanning electron microscope (SEM), a transmission electron microscope (TEM), etc., as long as it can capture microscope images of the nanocarbon network formed in the nanocarbon layer 113 and the individual nanocarbons included in the network. For example, in the present disclosure, it is assumed that the imaging device includes an AFM that can image the CNT network possessed by the nanocarbon layer 113 and the individual CNTs 42.

[0019] To evaluate the degree of orientation of the nanocarbon layer 113, it is desirable to be imaged in an observation region where d is made as large as possible so that there are a plurality of regions having a specific orientation direction (also referred to as "local orientation domains") within the observation region. In addition, it is desirable to gradually expand the observation region and observe it including the region where the orientation component asymptotically approaches a constant value. The orientation component asymptotically approaches a constant value S full as the observation region becomes larger. For example, in FIGS. 16, 18, 20, and 22 described later, it is considered that it can be confirmed that the orientation component (S_fit) asymptotically approaches a constant value (S full ). It is desirable that the observation region includes up to the region where the value of the orientation component becomes "0.2" or less. The orientation component is a constant value (Sfull ) In the observation region where it can be confirmed that it approaches, a state where the orientation of the oriented objects is aligned in a certain direction (a state where d is small) to a state where the orientation is somewhat random is observed. On the other hand, in the observation region where it has not been confirmed that the orientation component approaches a certain value (S full ) (in each observation region where exponential decay is observed at d < 2000 nm), the nanocarbon layer 113 having a value exceeding "0.2" of the orientation component value has a state where the orientation of the oriented objects is aligned in a certain direction within that observation region. Therefore, as a result of gradually expanding the observation region, assuming that it can be sufficiently confirmed that the value satisfies "less than or equal to 0.2" of the orientation component value and the orientation component approaches a certain value (S full ), it is desirable to set the observation region to a region where "d = 10000 nm" or more, or "d = 20000 nm" or more.

[0020] When imaging in an observation region with d as large as possible, since each individual CNT42 becomes unclear, the operator needs to perform image processing to emphasize the structure of each oriented object. The attenuation constant λ included in the orientation component c To obtain, as an image processing method, the processing of the flowchart shown in FIG. 3 is performed. First, the operator prepares a plurality of imaging images (hereinafter referred to as "AFM images") obtained by imaging the nanocarbon layer 113 having a network with an AFM (step ST91). In one AFM image, it may be difficult to obtain orientation data depending on the influence of noise on the image. Therefore, the operator prepares AFM images obtained by imaging the same oriented object a plurality of times as necessary.

[0021] Next, the operator performs contrast limited adaptive histogram equalization (CLAHE) processing on each AFM image (step ST92). When the CNT network has local unevenness, local light and darkness occur, and the structure of each CNT 42 forming the CNT network may become unclear. Therefore, CLAHE processing is performed to reduce the influence of local light and darkness. An example of the captured image is shown in FIG. 4, and an example of the image after histogram equalization processing is shown in FIG. 5.

[0022] Next, the operator aligns a plurality of captured images (step ST93). For example, in each AFM image, since there may be a deviation in the imaging position for each measurement, if averaging processing is performed as it is, the image will be blurry. Therefore, the operator aligns a plurality of images using an algorithm such as ACCELERATED-KAZE before averaging processing.

[0023] Next, the operator performs averaging processing on the aligned plurality of captured images to reduce noise (step ST94). An example of the image after averaging processing is shown in FIG. 6.

[0024] Next, the operator performs Gabor filter processing on the image after averaging processing with reduced noise to obtain the orientation data θ~ of each pixel shown in Equation (4) and the confidence w of the orientation shown in Equation (8) (step ST95).

Equation

Equation

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Number

Number

[0025] Next, the operator acquires a correlation image based on the confidence map in which the confidence w obtained by the Gabor filter process is stored in each pixel and the image after the averaging process (Step ST96). For example, the operator performs a correlation operation between the confidence map and the AFM image after the averaging process to acquire a correlation image. By this operation, it becomes possible to acquire an image in which a linear structure as shown in FIG. 7 is emphasized.

[0026] Next, the operator performs adaptive binarization and skeletonization of the correlation image (Step ST97). Specifically, the operator uses the correlation image obtained in step ST96 to convert it into a binary image through adaptive thresholding. Also, the operator may delete micro-regions from FIG. 7 as shown in FIG. 8 if necessary. After that, the operator performs skeletonization as shown in FIG. 9 to reduce the influence of the line thickness of the two-dimensional structure.

[0027] Next, the operator obtains the orientation data of the center line by performing a product operation between the orientation data obtained in step ST95 and the skeleton image (step ST98). Through the above process, the orientation data of the two-dimensional structure in units of 1 pixel is obtained. When the orientation angle and the average orientation direction n of each oriented object are derived from the orientation data obtained in step ST95 or the orientation data of the center line, the orientation parameter S 2D (d) (Equation (1)) is obtained. After that, the attenuation constant λ c is determined based on the relationship between the orientation component shown in Equation (3) and the size of the observation region determined by the size d of one side of the square observation region. As described above, as a result of gradually expanding the observation region, if it can be sufficiently confirmed that the value of the "orientation component is 0.2" or less and the orientation component asymptotically approaches a constant value (S full ), it is desirable to set the region of "d = 10000 nm" or more, or "d = 20000 nm" or more as the observation region.

[0028] (Film manufacturing method) An example of the film manufacturing method in the laminated structure 11 will be described. The film manufacturing method in the present disclosure is implemented according to the flow shown in FIG. 10. Supplementary diagrams for each flow are shown together in FIG. 11.

[0029] First, the operator determines whether the pre-treatment substrate has an insulating layer (step ST0). When the pre-treatment substrate does not have an insulating layer (step ST0: NO), the operator forms a base insulating layer 111X on the pre-treatment substrate to obtain a substrate 111 (step ST1B). As a method for forming the underlying insulating layer 111X, there are a method of heat-treating the substrate before processing and a method of directly forming the underlying insulating layer by CVD (Chemical Vapor Deposition). When the substrate before processing has an insulating layer (step ST0: YES), the operator uses the substrate before processing as the substrate 111 as it is and performs the process of the next step ST1.

[0030] Next, the operator performs surface modification of the substrate 111 (step ST1). Specifically, the operator performs ashing, ozone cleaning, etc. on the lamination surface 111L. For example, when the underlying insulating layer 111X is silicon oxide, a hydroxy group is formed on the lamination surface 111L by step ST1.

[0031] Next, the operator forms an initial self-assembled film (hereinafter referred to as "initial self-assembled film 112") that occupies most of the amount in the self-assembled film 112A on the substrate 111 (step ST2). Specifically, the operator immerses the substrate 111 in the dissolution solution 2α shown in FIG. 11 for a predetermined time to form an initial self-assembled film 112 on the lamination surface 111L. The formed initial self-assembled film 112 contains a silane coupling agent 22 for forming the nanocarbon layer 113 on the substrate 111.

[0032] (Dissolution solution) In the dissolution solution 2α (2β) shown in FIG. 11, the silane coupling agent 22 is dissolved in the dispersion medium 21. For example, the dissolution solution 2α and the dissolution solution 2β have different concentrations of the silane coupling agent 22 in the dissolution solution. For example, the concentration of the silane coupling agent 22 in the dissolution solution 2α is 0.01 to 0.1%. For example, the concentration of the silane coupling agent 22 in the dissolution solution 2β is 0.025 to 5%. For example, the dispersion medium 21 is pure water, ethanol, or an organic solvent such as toluene. Examples of the silane coupling agent 22 include 3-aminopropyltriethoxysilane (APTES), 3-aminopropyltrimethoxysilane, 3-aminopropylmethyltriethoxysilane, 3-aminopropylmethyltrimethoxysilane, and the like. For example, the operator may use a silane coupling agent 22 having an amino group to improve the adhesion of the CNT 42 described later.

[0033] Next, the operator performs primary drying on the formed initial self-assembled film 112 (step ST3). For example, the operator may use a spin coater 7 for drying the initial self-assembled film 112 (primary drying). Specifically, the operator takes out the immersed substrate 111 and then rotates the substrate 111 with the spin coater 7 to dry (primary dry) the initial self-assembled film 112. As shown in FIG. 11, with the spin coater 7, the substrate 111 rotates in one direction (ROT direction) around the rotation axis AX.

[0034] Next, the operator washes the primarily dried initial self-assembled film 112 with the cleaning liquid 3 (step ST4). For example, pure water or ultrapure water may be used as the cleaning liquid 3. Specifically, the operator washes the substrate 111 with ultrapure water. For example, the operator may use ultrasonic waves for washing the substrate 111. By washing, the operator separates a weak bond such as van der Waals force in the bond between the substrate 111 and the initial self-assembled film 112. Note that step ST4 may not be performed if the amount of the silane coupling agent 22 adhering to the primarily dried initial self-assembled film 112 is sufficiently small compared to the amount of the silane coupling agent 22 contained in the dissolution liquid 2β described later in step ST6. The same applies to step ST5, which is a post-treatment of step ST4.

[0035] Next, the operator dries the washed initial self-assembled film 112 (step ST5). For example, the operator performs a drying process similar to that in step ST3. The rotation speed of the spin coater may be appropriately adjusted for each step.

[0036] Next, as shown in FIG. 11, the operator forms a self-assembled film 112A by immersing the initial self-assembled film 112 formed on the substrate 111 in a solution 2β in which the silane coupling agent 22 is dissolved (step ST6). When steps ST4 and ST5 are performed, in step ST6, the operator immerses the washed initial self-assembled film 112 as the dried (primary drying) initial self-assembled film 112 in the solution 2β. After immersion, the self-assembled film 112A with the amount of the initial self-assembled film 112 formed on the lamination surface 111L adjusted is obtained. That is, in step ST6, the amount of the silane coupling agent 22 contained in the self-assembled film 112A changes compared to the initial self-assembled film 112 formed in step ST2. The degree of orientation of the self-assembled film 112A changes depending on its amount. In other words, by adjusting the concentration of the solution 2β, the degree of orientation of the self-assembled film 112A is controlled. Thereby, the local degree of orientation of the nanocarbon contained in the nanocarbon layer 113 is suppressed.

[0037] Next, the operator dries (secondary drying) the self-assembled film 112A formed on the substrate 111 after immersion in the solution 2β (step ST7). For example, the operator performs a drying process similar to that in step ST3 and step ST5. The rotation speed of the spin coater may be appropriately adjusted for each step. For example, in step ST7, the self-assembled film 112A is dried at a rotation speed of 1000 rpm or more and 4000 rpm or less by a spin coater.

[0038] Next, the operator laminates a nanocarbon layer 113 on the dried (secondary drying) self-assembled film 112A (step ST8). Specifically, the operator drops the dispersion liquid 4 from the nozzle 5 onto the self-assembled film 112A and allows it to stand for a predetermined time. Thereby, the nanocarbon layer 113 is laminated. For example, the nozzle 5 is included in a dispenser, an inkjet, or the like.

[0039] (Dispersion liquid) The dispersion liquid 4 includes a dispersion medium 41, CNTs 42, and a surfactant 43. For example, ultrasonic treatment is used for the mixing performed when preparing the dispersion liquid 4. For example, the dispersion liquid 4 includes CNTs 42 with a concentration of 0.001 to 0.3 mass% and a surfactant 43 with a concentration of 0.01 to 1 mass%. When laminating the nanocarbon layer 113, the operator can sufficiently disperse the CNTs 42 in the dispersion liquid 4 by using the surfactant 43. Also, the surfactant 43 may be nonionic. Nonionic surfactants are more easily removed by heat treatment or the like than ionic surfactants. For example, as the nonionic surfactant, there is a polyoxyethylene alkyl ether solution such as polyoxyethylene (100) stearyl ether or polyoxyethylene (23) lauryl ether. The dispersion medium 41 is not particularly limited as long as it is a solvent capable of dispersing and suspending the CNTs 42 in the dispersion liquid 4. For example, water, heavy water, an organic solvent, an ionic liquid, or a mixture thereof can be used. By subjecting the dispersion liquid 4 to ultrasonic treatment, the operator can sufficiently separate the aggregated metallic CNTs and semiconducting CNTs. In addition, the operator can appropriately control the length of the CNTs 42 by controlling the output and treatment time of the ultrasonic waves in the ultrasonic treatment. For example, the operator may separate and remove the metallic CNTs and semiconducting CNTs that were not dispersed by ultrasonic treatment by ultracentrifugation. For example, in ultracentrifugation, the operator may remove those that are not useful for the electrical characteristics of the manufactured bolometer, such as bundles of CNTs and amorphous carbon contained in the dispersion liquid 4. For example, a dispersion liquid 4 in which a surfactant 43, a metallic CNT, and a semiconducting CNT are uniformly dispersed in a dispersion medium 41 may be used. For example, in order to obtain a high TCR in a bolometer, a semiconducting CNT may be separated or concentrated and used.

[0040] Next, the operator washes the substrate 111 on which the nanocarbon layer 113 is laminated with the cleaning liquid 3 (step ST9). For example, pure water or ultrapure water may be used as the cleaning liquid 3. Specifically, the operator washes the substrate 111 with ultrapure water. For example, the operator may use ultrasonic waves for washing the substrate 111.

[0041] Next, the operator dries the washed substrate 111 (step ST10). For example, the operator performs a drying process similar to that in step ST3, step ST5, and step ST7. The rotation speed of the spin coater may be appropriately adjusted for each step.

[0042] Next, the operator heats the dried substrate 111 (step ST11). Specifically, the operator accommodates the substrate 111 in the chamber 6 and heats it at 180°C for 2 h. By these operations, a nanocarbon layer 113 with a suppressed local orientation degree of nanocarbon is formed on the substrate 111. Further, the operator may additionally heat the substrate 111 in an environment of 300°C to 400°C in order to remove surfactant components that may inhibit electrical conduction.

[0043] Next, the operator checks the orientation degree of the nanocarbon layer 113 (step ST12). For example, the operator uses the attenuation constant λ c described above to check the orientation degree of the nanocarbon layer 113. (End)

[0044] (Function and effect) According to the film manufacturing method of the present disclosure, the initial self-assembled film 112 is immersed in the solution 2β containing the silane coupling agent 22. Thereby, the amount of the initial self-assembled film 112 can be adjusted, and the orientation of the self-assembled film 112A can be controlled. That is, the operator can control the orientation of the organic molecules contained in the self-assembled film 112A, and can control the degree of orientation of the nanocarbon layer 113 laminated on the substrate 111 through the self-assembled film 112A. Therefore, the film manufacturing method according to the present disclosure is easy to control the degree of orientation.

[0045] In addition, the film manufacturing method of the present disclosure can separate a weak bond such as the van der Waals force in the bond between the substrate 111 and the initial self-assembled film 112 by washing the dried (primary drying) initial self-assembled film 112. Thereby, it becomes easier to adjust the amount of the initial self-assembled film 112, and the effect that the orientation of the self-assembled film 112A can be more easily controlled is achieved.

[0046] In addition, the film manufacturing method of the present disclosure includes "a step of forming a self-assembled film (initial self-assembled film 112) on a substrate (step ST2), a step of drying the self-assembled film (initial self-assembled film 112) (step ST3), a step of washing the self-assembled film (initial self-assembled film 112) using the cleaning liquid 3 (step ST4), a step of drying the washed self-assembled film (initial self-assembled film 112) (step ST5), a step of immersing the substrate 111 in the solution 2β in which the silane coupling agent 22 is dissolved (step ST6), a step of drying the substrate 111 after immersion in the solution 2β (step ST7), and a step of laminating a nanocarbon layer on the self-assembled film 112A (step ST8)", and the following effects can be obtained. Due to these invention specific matters, the operator can control the orientation of the organic molecules contained in the self-assembled film 112A, and can control the degree of orientation of the nanocarbon layer 113 laminated on the substrate 111 through the self-assembled film 112A. Therefore, the effect of "the film manufacturing method according to the present disclosure can easily control the degree of orientation" can be obtained.

[0047] In addition, in the film manufacturing method of the present disclosure, further, due to "the silane coupling agent 22 has an amino group", in addition to the effect of "the silanol group of the silane coupling agent 22 can strengthen the bond with CNT", the effect of "the self-assembled film 112A can strengthen the bond with the substrate 111. For example, when the underlayer insulating layer 111X is SiO 2 a stronger bond is formed." can also be obtained.

[0048] In addition, in the film manufacturing method of the present disclosure, further, due to "the silane coupling agent 22 is 3-aminopropyltriethoxysilane", the effect of "among the silane coupling agents 22, the bond with CNT can be made stronger" can also be obtained.

[0049] In addition, in the film manufacturing method of the present disclosure, further, due to "the concentration of the silane coupling agent 22 in the solution 2β is 0.025 to 5%", the effect of "it is easy to control the degree of orientation of the nanocarbon layer 113 laminated on the substrate 111" can also be obtained.

[0050] In addition, in the film manufacturing method of the present disclosure, further, due to "the nanocarbon layer contains carbon nanotubes", the effect of "it is easy to form a network structure by carbon nanotubes and it is easy to reduce the resistance value of the laminated structure 11" can also be obtained.

[0051] In addition, in the film manufacturing method of the present disclosure, further, due to "the nanocarbon layer 113 is laminated using the surfactant 43", the effect of "since the dispersibility of CNT42 is improved, it is difficult to aggregate, and it is easy to control the degree of orientation of the nanocarbon layer 113 laminated on the substrate 111 through the self-assembled film 112A." can also be obtained.

[0052] In the laminated structure 11 of the present disclosure, "it includes a base material 111, a self-assembled film 112A, and a nanocarbon layer 113 having an orientation parameter. The orientation parameter has an oriented component and a random component, and the oriented component is an attenuation constant λ related to the local degree of orientation c with the side length d of one side of the square observation region of the nanocarbon layer 113 and a constant value S full and is represented by Equation (3) which is a function of, and the attenuation constant λ c is 300 nm or more

Equation

[0053] In addition, since the orientation of the network structure affects the electrical resistance, by quantitatively grasping the orientation of the network structure, the orientation of the network structure and the electrical resistance can be associated via the attenuation constant λ c , and the overall resistance value of the network structure can also be evaluated.

[0054] In addition, in the laminated structure 11 of the present disclosure, further, "the oriented component asymptotically approaches a constant value S full as the observation region increases", so that "by gradually expanding the observation region, since the oriented component decays exponentially, it is easy to grasp that the degree of orientation is controlled by the attenuation constant λ c ". The effect can also be obtained.

[0055] In the above-described laminated structure 11, the base material 111 is a Si substrate, but it may also be an insulating material. Thereby, it is also applicable to elements such as a bolometer having a diaphragm.

[0056] In the above-described laminated structure 11, the nanocarbon layer 113 contains CNTs, but it may also contain CNBs. CNB has a shape in which single-layer carbon nanohorns are radially assembled and extend in a fibrous shape. CNB is a nanocarbon having both high conductivity and high dispersibility, which are characteristics of CNTs and CNHs. Thereby, the degree of orientation of the nanocarbon layer 113 laminated on the base material 111 via the self-assembled film 112A can be controlled in the same manner as in the case of CNT42.

[0057] In the above-described film manufacturing method, instead of the silane coupling agent 22 contained in the dissolution liquid 2β, a material having an amino group and a silanol group may be used. Even if this material is used instead of the silane coupling agent 22, the adhesion of CNT42 is promoted by the amino group, and the bonding between the base material 111 and the self-assembled film 112A is strengthened by the silanol group. Thereby, the same effect as the suppression of the degree of orientation of the nanocarbon layer 113 using the silane coupling agent 22 of the present disclosure can be obtained.

[0058] In the above disclosure, by controlling the orientation of the organic molecules contained in the self-assembled film 112A of the laminated structure 11, the degree of orientation of the nanocarbon layer 113 laminated on the base material 111 via the self-assembled film 112A can be controlled. Thereby, it is disclosed that the laminated structure 11 of the above disclosure is easy to control the degree of orientation. On the other hand, the bolometer in the following disclosure includes a laminated structure 11C in a light receiving portion that detects infrared rays. The bolometer according to the present embodiment focuses on the fact that, depending on the distance between the electrodes to be connected, a network conductive path in the nanocarbon layer is easily formed because the nanocarbon layer has a predetermined degree of orientation, and the resistance value is easily reduced. Hereinafter, an example of the bolometer in the present disclosure will be described with reference to FIG. 12. Note that the same reference numerals are assigned to the components common to the above disclosure, and the detailed description thereof is omitted.

[0059] The bolometer 1 is used as a sensor for detecting infrared rays. The bolometer 1 includes a laminated structure 11C and an electrode 12. The laminated structure 11C includes a base material 111, a self-assembled film 112A with an adjusted amount of the initial self-assembled film 112, and a nanocarbon layer 113 in this order. For example, the base material 111 included in the laminated structure 11C is an insulating material. For example, the laminated structure 11C may include the initial self-assembled film 112 on a part of the laminated surface 111L. In that case, the nanocarbon layer may be present on a part of the base material 111.

[0060] (Electrode) The electrode 12 is electrically connected to the nanocarbon layer 113. The electrode 12 is a pair of electrodes (first electrode 12a, second electrode 12b) sandwiching the laminated structure 11C. For example, the electrode 12 may be formed so that the pair of electrodes sandwich a laminated structure 11C or a part thereof that includes the base material 111, the self-assembled film 112A, and the nanocarbon layer 113 in this order. For example, in the present disclosure, the electrode 12 is formed so as to sandwich the self-assembled film 112A and the nanocarbon layer 113 included in the laminated structure 11C. The thickness of the electrode 12 can be adjusted as appropriate. For example, the thickness of the electrode 12 is 10 nm to 1.0 mm. For example, the thickness of the electrode 12 is 50 nm to 1.0 μm. The distance between the pair of electrodes (first electrode 12a, second electrode 12b) can be adjusted as appropriate. For example, when having the laminated structure 11C and the pair of electrodes 12 as in the bolometer 1, the attenuation constant λ c With respect to, when the distance between the pair of electrodes (first electrode 12a, second electrode 12b) is small, depending on whether the direction of the electrode 12 is parallel or perpendicular to the orientation direction of the nanocarbon layer 113, the overall resistance value of the network structure may change greatly, and the overall resistance value may be difficult to stabilize. On the other hand, the attenuation constant λc When the distance between a pair of electrodes is large, the alignment direction is uniform, so the overall resistance value of the network structure is likely to be stable. For example, the distance between a pair of electrodes (the first electrode 12a and the second electrode 12b) is 1.0 μm to 50 μm. For example, the distance between a pair of electrodes (the first electrode 12a and the second electrode 12b) is 5.0 μm to 20 μm. For example, the electrode 12 is an electrode made of Au, Al, Ti, or an alloy mainly composed of these. Each of the electrodes 12 (the first electrode 12a and the second electrode 12b) may include an underlayer for the electrode. The underlayer may be a layer containing Ti. As an example, the electrode 12 of the present disclosure is an electrode in which an Au layer is laminated via a Ti layer as an underlayer.

[0061] (Function and Effect) According to the present embodiment, by controlling the orientation of the organic molecules contained in the self-assembled film 112A of the laminated structure 11C, the degree of orientation of the nanocarbon layer 113 laminated on the substrate 111 can be controlled via the self-assembled film 112A. Therefore, the laminated structure 11C according to the present disclosure is easy to control the degree of orientation.

[0062] Also, depending on the distance between the connected electrodes, when the nanocarbon layer has a predetermined degree of orientation, a network conductive path in the nanocarbon layer is likely to be formed, and the resistance value is likely to be reduced.

[0063] In the bolometer 1 disclosed above, the laminated structure 11C may have a laminated end face 11Ce from which the nanocarbon layer 113 is cut out. As an example, it is conceivable that it is cut out by an etching process or the like from a part of the substrate 111 across the nanocarbon layer 113. As another example, it may be cut out from the self-assembled film 112A across the nanocarbon layer 113. When performing an etching process, a protective layer for preventing damage by etching may be formed on the nanocarbon layer 113. After cutting, the electrode 12 may be electrically connected to the nanocarbon layer 113 exposed from the cut laminated end face 11Ce.

[0064] Hereinafter, an example of the configuration of the laminated structure in the present disclosure will be described with reference to FIG. 13.

[0065] (Configuration) The laminated structure 11m sequentially includes a base material 111m, a self-assembled film 112Am, and a nanocarbon layer 113m having an orientation parameter. The orientation parameter has an orientation component and a random component, and the orientation component is an attenuation constant λ related to the local degree of orientation c with the side length d of one side of the square observation region of the nanocarbon layer 113m and a constant value S full and is represented by Equation (3) which is a function of, and the attenuation constant λ c is 300 nm or more.

Equation

[0066] (Function and Effect) According to the laminated structure 11m of the present disclosure, the orientation of the network structure of the nanocarbon layer 113m laminated on the base material 111m via the self-assembled film 112Am can be selected at a predetermined degree of orientation with the attenuation constant λ c . As a result, a laminated structure 11m with the degree of orientation controlled by the self-assembled film 112Am having a specific amount can be obtained. Therefore, the laminated structure 11m of the present disclosure is easy to control the degree of orientation.

[0067] In addition, since the orientation of the network structure affects the electrical resistance, by quantitatively grasping the orientation of the network structure, the orientation of the network structure and the electrical resistance can be associated via the attenuation constant λ c , and the overall resistance value of the network structure can also be evaluated.

[0068] Hereinafter, an example of the film manufacturing method in the present disclosure will be described with reference to FIG. 14. The film manufacturing method in the present disclosure is implemented according to the flow shown in FIG. 14.

[0069] The method for manufacturing a film includes a step of forming an initial self-assembled film on a substrate (step ST10), a step of primarily drying the formed initial self-assembled film (step ST20), a step of forming a self-assembled film by immersing the primarily dried initial self-assembled film in a solution in which a silane coupling agent is dissolved (step ST30), a step of secondarily drying the formed self-assembled film (step ST40), and a step of laminating a nanocarbon layer on the secondarily dried self-assembled film (step ST50).

[0070] (Function and Effect) According to the method for manufacturing a film of the present disclosure, the orientation of the self-assembled film can be controlled by immersing the self-assembled film in a solution containing a silane coupling agent. That is, an operator can control the orientation of organic molecules contained in the self-assembled film and control the degree of orientation of the nanocarbon layer laminated on the substrate through the self-assembled film. Therefore, the method for manufacturing a film of the present disclosure can easily control the degree of orientation.

Example

[0071] Hereinafter, the effects of the present disclosure will be further specifically described by way of examples. The conditions in the examples are one set of conditions adopted for confirming the feasibility and effects of the present disclosure, and the present disclosure is not limited to this one set of conditions. The present disclosure can adopt various conditions as long as it does not deviate from the gist of the present disclosure and achieves the object of the present disclosure.

[0072] Elements N (N = I - V) to be evaluated were prepared about 16 for each of elements I - V by the method for manufacturing a film disclosed above. Element N includes a laminated structure 11 and a new pair of electrodes 12. Element N has an underlying insulating layer and includes an initial self-assembled film 112 on a part of a substrate 111. The nanocarbon layer 113 exists on a part of the substrate 111. The distance between the pair of electrodes (first electrode 12a and second electrode 12b) is 8 μm, and the CNTs 42 included in the nanocarbon layer 113 electrically connect between the electrodes over the longitudinal direction 640 μm of the electrodes.

[0073] When fabricating the element N, the concentration of the silane coupling agent 22 in the dissolution solution 2α was 0.01 to 0.1%. When fabricating the element N, the concentration of the silane coupling agent 22 in the dissolution solution 2β was 0.001 to 5%. When fabricating the element N, the dispersion liquid 4 contained CNTs 42 with a concentration of 0.001 to 0.3 mass% and a surfactant 43 with a concentration of 0.01 to 1 mass%.

[0074] The concentration of the silane coupling agent 22 (APTTES) in the dissolution solution 2β was as follows. The concentration of APTES used for fabricating the element I in FIGS. 16 - 17 was 0.001%. The concentration of APTES used for fabricating the element II in FIGS. 18 - 19 was 0.025%. The concentration of APTES used for fabricating the element III in FIGS. 20 - 21 was 0.1%. The concentration of APTES used for fabricating the element IV in FIG. 22 was 2.0%. The concentration of APTES used for fabricating the element V in FIG. 23 was 0.05%. The vertical axis represents the values of each component (orientation component and random component) of the orientation parameter, and the horizontal axis represents the size of the observation region determined by the size d of one side of the square observation region. Since the orientation parameter is expressed as the sum of two components, the orientation component and the random component, the components of the orientation parameter were compared with each other. In each of FIGS. 16, 18, 20, and 22, in the observation region where "the value of the orientation component is 0.2" or less, it was confirmed that the value of the orientation component (S_fit) approaches a constant value (S full ). Regarding the random component (S_random), it was confirmed that the orientation component in each observation region exponentially decays as a whole and has the same decay rate regardless of the concentration of APTES. Therefore, it was estimated that an index of the degree of orientation can be known by observing the decay tendency of the orientation component in the orientation parameter. Figure 24 shows the relationship between the concentration of APTES and the attenuation constant λ c and it was confirmed that as the concentration of APTES increases, the attenuation constant λ c becomes a large value. Even at a concentration of 5% of APTES in the lysate 2β, it was confirmed that the attenuation constant λ c becomes even larger. Therefore, it was shown that λ c obtained in the present disclosure can be used as a quantitative index of the degree of orientation. From the AFM images of the four CNT networks in FIGS. 17, 19, 21, and 23, it can be seen that as the concentration of APTES decreases, the local CNT orientation is eliminated. FIG. 25 is a diagram comparing the overall resistance values of the CNT networks in the element N. It was confirmed that the larger the attenuation constant λ c , the smaller the overall resistance value. The coefficient of variation is obtained by dividing the standard deviation of the overall resistance values of each element N created in groups of 16 by the average of the overall resistance values. From the concentration of APTES used in the creation of element I: 0.001% to the concentration of APTES used in the creation of element II: 0.025%, the coefficient of variation remains relatively high, but since the overall resistance value decreases across digits as the concentration of APTES increases, it was confirmed that a laminated structure having a CNT network with an attenuation constant λ c of 300 nm or more is desirable.

[0075] The present disclosure has been described above with reference to the embodiments, but the present disclosure is not limited to the above-described embodiments. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present disclosure within the scope of the present disclosure. And each embodiment can be combined with other embodiments as appropriate.

[0076] Some or all of the above embodiments can be described as follows in the appended claims, but are not limited thereto.

[0077] (Appended Claim 1) A step of forming an initial self-assembled film on a substrate, and The step of subjecting the formed initial self-assembled film to primary drying; The step of forming a self-assembled film by immersing the initially self-assembled film that has been subjected to primary drying in a solution in which a silane coupling agent is dissolved; The step of subjecting the formed self-assembled film to secondary drying; The step of laminating a nanocarbon layer on the self-assembled film that has been subjected to secondary drying; A film manufacturing method comprising the above steps.

[0078] (Appendix 2) The method further includes the step of washing the initially self-assembled film that has been subjected to primary drying, In the step of immersion, the washed initially self-assembled film is immersed as the initially self-assembled film that has been subjected to primary drying The film manufacturing method according to claim 1.

[0079] (Appendix 3) The silane coupling agent has an amino group The film manufacturing method according to Appendix 1 or Appendix 2.

[0080] (Appendix 4) The silane coupling agent is 3-aminopropyltriethoxysilane The film manufacturing method according to Appendix 1 or Appendix 2.

[0081] (Appendix 5) In the solution, the concentration of the silane coupling agent is 0.025 to 5% The film manufacturing method according to Appendix 1 or Appendix 2.

[0082] (Appendix 6) The nanocarbon layer contains carbon nanotubes The film manufacturing method according to Appendix 1 or Appendix 2.

[0083] (Appendix 7) The nanocarbon layer is laminated using a surfactant The film manufacturing method according to Appendix 5.

[0084] (Appendix 8) It sequentially includes a base material, a self-assembled film, and a nanocarbon layer having an orientation parameter. The orientation parameter has an orientation component and a random component. The orientation component is an attenuation constant λ related to the local degree of orientation, c the size d of one side of the square observation region of the nanocarbon layer, and a constant value S full and is represented by formula (3) which is a function of them. The attenuation constant λ c is 300 nm or more. Laminated structure.

Number

[0085] (Appendix 9) As the observation region becomes larger, the orientation component asymptotically approaches the constant value S full Laminated structure according to Appendix 8. The laminated structure according to Appendix 8.

[0086] (Appendix 10) The laminated structure according to Appendix 8 or Appendix 9, and an electrode electrically connected to the nanocarbon layer, comprising Bolometer.

Explanation of Signs

[0087] 1 Bolometer 2α Dissolution solution 2β Dissolution solution 3 Cleaning solution 4 Dispersion solution 5 Nozzle 6 Chamber 7 Spin coater 11 Laminated structure 11C Laminated structure 11Ce End face of the laminated structure 11m Laminated structure 12 Electrode 12a First electrode 12b Second electrode 21 Dispersion medium 22 Silane coupling agent 41 Dispersion medium 42 CNT 43 Surfactant 111 Substrate 111L Laminated surface 111m Substrate 111X Underlying insulating layer 112 Initial self-assembled film 112A Self-assembled film 112Am Self-assembled film 113 Nanocarbon layer 113m Nanocarbon layer S 2D Orientation parameter λ c Attenuation constant d The length of one side of the observed square region S full Constant value

Claims

1. Forming an initial self-assembled film on a substrate; Primarily drying the formed initial self-assembled film; Forming a self-assembled film by immersing the primarily dried initial self-assembled film in a solution in which a silane coupling agent is dissolved; Secondarily drying the formed self-assembled film; Laminating a nanocarbon layer on the secondarily dried self-assembled film; A film manufacturing method comprising the above steps.

2. Further comprising the step of washing the primarily dried initial self-assembled film, In the step of immersing, as the primarily dried initial self-assembled film, the washed initial self-assembled film is immersed. The film manufacturing method according to Claim 1.

3. The silane coupling agent has an amino group. The film manufacturing method according to Claim 1 or Claim 2.

4. The silane coupling agent is 3-aminopropyltriethoxysilane. The film manufacturing method according to Claim 1 or Claim 2.

5. In the solution, the concentration of the silane coupling agent is 0.025 to 5%. The film manufacturing method according to Claim 1 or Claim 2.

6. The nanocarbon layer includes carbon nanotubes. The film manufacturing method according to Claim 1 or Claim 2.

7. The nanocarbon layer is laminated using a surfactant. The film manufacturing method according to Claim 5.

8. Comprising a substrate, a self-assembled film, and a nanocarbon layer having an orientation parameter in this order, The orientation parameter has an oriented component and a random component, The alignment component is an attenuation constant λ related to the local degree of alignment ｃ with the size d of one side of the square observation region of the nanocarbon layer and a constant value S ｆｕｌｌ and is represented by Expression (3) which is a function of these the attenuation constant λ ｃ is 300 nm or more, A laminated structure. 【Mathematics 3】

9. The alignment component approaches the constant value S as the observation region becomes larger ｆｕｌｌ asymptotically The laminated structure according to Claim 8.

10. The laminated structure according to Claim 8 or Claim 9, and An electrode electrically connected to the nanocarbon layer, Comprising A bolometer.

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