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WO2018030182A1 - Agrégat de nanotubes de carbone - Google Patents

Agrégat de nanotubes de carbone Download PDF

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Publication number
WO2018030182A1
WO2018030182A1 PCT/JP2017/027492 JP2017027492W WO2018030182A1 WO 2018030182 A1 WO2018030182 A1 WO 2018030182A1 JP 2017027492 W JP2017027492 W JP 2017027492W WO 2018030182 A1 WO2018030182 A1 WO 2018030182A1
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WIPO (PCT)
Prior art keywords
carbon nanotube
aggregate
nanotube aggregate
carbon nanotubes
carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2017/027492
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English (en)
Japanese (ja)
Inventor
義治 畠山
智昭 市川
将太郎 増田
前野　洋平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017069814A external-priority patent/JP7051300B2/ja
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to EP17839255.1A priority Critical patent/EP3498669A4/fr
Priority to CN201780049407.5A priority patent/CN109562945A/zh
Priority to KR1020197003788A priority patent/KR102477740B1/ko
Priority to US16/324,759 priority patent/US20190177165A1/en
Publication of WO2018030182A1 publication Critical patent/WO2018030182A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes

Definitions

  • the present invention relates to an aggregate of carbon nanotubes.
  • the conventional conveyance fixing jig has a problem that the workpiece is held by an elastic material such as a resin, and the elastic material is likely to adhere and remain on the workpiece.
  • an elastic material such as a resin has a problem that heat resistance is low, and grip force is reduced under a high temperature environment.
  • the conveyance fixture composed of such a material has a problem that the gripping force is essentially low and the workpiece cannot be sufficiently held even at room temperature.
  • a method of holding the workpiece under a high temperature environment there are a method of suctioning under reduced pressure, a method of fixing the workpiece by the shape of the conveyance fixing jig (for example, chucking, counterboring, etc.) and the like.
  • the method of adsorbing under reduced pressure is effective only under an air atmosphere and cannot be employed under vacuum in a CVD process or the like.
  • the method of fixing the workpiece by the shape of the conveyance fixing jig there is a problem that the workpiece is damaged or particles are generated due to contact between the workpiece and the conveyance fixing jig.
  • a carbon nanotube aggregate is usually a method in which a catalyst layer is formed on a predetermined substrate, a carbon source is filled in a state where the catalyst is activated by heat, plasma, etc., and carbon nanotubes are grown (chemical vapor phase). (Growth method). According to such a manufacturing method, a carbon nanotube aggregate composed of carbon nanotubes oriented substantially vertically from the base material can be obtained.
  • the carbon nanotube aggregate When the carbon nanotube aggregate is applied to the conveyance fixing jig, the carbon nanotube aggregate obtained as described above is taken out from the base material and fixed on the conveyance fixing jig.
  • carbon nanotubes are bundled by the action of van der Waals force, and the connection in the surface direction is very weak, and the carbon nanotubes are easily separated. Is difficult.
  • An object of the present invention is to provide a carbon nanotube aggregate that is excellent in gripping force and can maintain a sheet shape.
  • the aggregate of carbon nanotubes of the present invention is composed of a plurality of carbon nanotubes in a sheet shape, and has a non-oriented portion of the carbon nanotubes.
  • the carbon nanotube aggregate further has an alignment portion of the carbon nanotube.
  • the said non-orientation part exists in the edge part vicinity of the length direction of the said carbon nanotube aggregate.
  • the length of the non-orientation part located in the vicinity of the end part in the length direction is 0.5 ⁇ m or more.
  • the maximum static friction coefficient at 23 ° C. of the surface on which the non-oriented portion is formed is 1.0 or more.
  • the aggregate of carbon nanotubes does not have the alignment portion of the carbon nanotube.
  • the carbon nanotube aggregate has a thickness of 10 ⁇ m to 5000 ⁇ m.
  • a sheet is provided. This sheet is composed of the carbon nanotube aggregate.
  • FIG. 1 is a schematic cross-sectional view of a carbon nanotube aggregate according to an embodiment of the present invention.
  • 2 is an SEM image of a carbon nanotube assembly according to one embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of a carbon nanotube aggregate according to another embodiment of the present invention. It is a schematic sectional drawing of the manufacturing apparatus of the carbon nanotube aggregate in one embodiment of this invention.
  • FIG. 1 is a schematic cross-sectional view schematically showing a part of a carbon nanotube aggregate according to an embodiment of the present invention.
  • the carbon nanotube aggregate 100 is composed of a plurality of carbon nanotubes 10 in a sheet shape.
  • the carbon nanotube aggregate 100 has a non-oriented portion 110 of the carbon nanotube 10.
  • the carbon nanotube aggregate 100 further includes an alignment portion 120 of the carbon nanotube 10.
  • the orientation portion 120 of the carbon nanotube 10 is oriented in a substantially vertical direction with respect to a predetermined plane (for example, one surface of the aggregate of carbon nanotubes defined at the ends of the plurality of carbon nanotubes).
  • the “substantially vertical direction” means that the angle with respect to the predetermined plane is preferably 90 ° ⁇ 20 °, more preferably 90 ° ⁇ 15 °, still more preferably 90 ° ⁇ 10 °, particularly The angle is preferably 90 ° ⁇ 5 °.
  • the non-orientation portion 110 of the carbon nanotube 10 exists in the vicinity of the end portion of the carbon nanotube aggregate 100 in the length direction.
  • a non-oriented portion 110 is formed at one end of the carbon nanotube aggregate 100.
  • the non-oriented portions of the carbon nanotubes may exist in the vicinity of both ends in the length direction of the carbon nanotube aggregate.
  • the non-oriented portion of the carbon nanotube may exist in the vicinity of the middle portion of the carbon nanotube aggregate.
  • the aggregate of carbon nanotubes may include a plurality of non-oriented portions and oriented portions of the carbon nanotubes.
  • the non-oriented portion of the carbon nanotube means an aggregate portion of carbon nanotubes having an orientation angle deviation value of 40 ° or more.
  • the deviation value of the orientation angle of the carbon nanotube is obtained as follows. (1) An SEM image (magnification of 20,000 times, image range: thickness of carbon nanotube aggregate ⁇ width of about 6 ⁇ m) of a cross section of the carbon nanotube aggregate is acquired.
  • FIG. 2 is an SEM image showing the lower surface 102 side of the carbon nanotube aggregate.
  • the surfaces defined by the ends of the plurality of carbon nanotubes and having 10 or more carbon nanotubes in the width direction are defined as the upper surface and the lower surface 102.
  • the deviation value of the orientation angle of the carbon nanotubes can be measured after forming the carbon nanotube aggregate on the substrate and before collecting the carbon nanotube aggregate from the substrate.
  • the lower surface of the carbon nanotube aggregate is a surface substantially parallel to the base material.
  • Lines 210 are drawn every 500 nm in parallel with the lower surface 102 from the lower surface 102 to set sections with an interval of 500 nm.
  • FIG. 2 shows a state in which up to 15 lines are drawn (a state in which 15 sections are set).
  • a circle 220 containing the carbon nanotube is set.
  • the circle 220 is set so that the straight line 230 connecting the two ends of the carbon nanotubes in contact with the circle is 500 nm ⁇ 50 nm in the section.
  • the orientation angle with respect to the lower surface 102 of the straight line 230 is measured, and the standard deviation of the orientation angle is determined from the angles of the ten carbon nanotubes in the compartment.
  • the standard deviation of the orientation angle is 40 ° or more, the carbon nanotubes in the section are not oriented, and the section is determined to be the non-oriented portion 110 of the carbon nanotube.
  • the non-orientation portion 110 has a thickness of 4 ⁇ m.
  • the non-oriented portion of the carbon nanotube may be simply referred to as a non-oriented portion.
  • the orientation portion of the carbon nanotube means an aggregate portion of carbon nanotubes having an orientation angle deviation value of less than 40 °. That is, as described above, the standard deviation of the orientation angle of the carbon nanotube is obtained for each predetermined section. When the standard deviation is less than 40 °, the carbon nanotube in the section is oriented, and the section is It is judged that it is an orientation part.
  • the alignment portion of the carbon nanotube is sometimes simply referred to as an alignment portion.
  • FIG. 3 is a schematic cross-sectional view schematically showing an aggregate of carbon nanotubes according to another embodiment of the present invention.
  • the carbon nanotube aggregate 100 ′ does not have the orientation part 120 of the carbon nanotube aggregate 100, and the whole is composed of the non-orientation part 110 of the carbon nanotube.
  • the carbon nanotube aggregate has the non-oriented portion of the carbon nanotube, whereby the connection in the plane direction is strengthened.
  • the carbon nanotube aggregate can be configured in a sheet shape.
  • the carbon nanotube aggregate composed of the aligned portion and the non-oriented portion of the carbon nanotube is a carbon nanotube aggregate composed of only the non-oriented portion of the carbon nanotube (The adhesiveness may be superior to that of FIG. This is considered to be due to the difference in the production method of the carbon nanotube aggregate, specifically, the presence or absence of compression during production (details will be described later).
  • the thickness of the non-oriented portion is preferably 0.5 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 20 ⁇ m, and further preferably 2 ⁇ m to 10 ⁇ m. Particularly preferably, it is 2 ⁇ m to 7 ⁇ m. If it is such a range, the carbon nanotube aggregate which is excellent in adhesiveness and can maintain a sheet
  • the ratio of the thickness of the non-oriented portion is relative to the thickness of the carbon nanotube aggregate (the sum of the thickness of the oriented portion and the thickness of the non-oriented portion).
  • it is 0.001% to 50%, more preferably 0.01% to 40%, still more preferably 0.05% to 30%, and particularly preferably 0.1% to 20%. . If it is such a range, the carbon nanotube aggregate which is excellent in adhesiveness and can maintain a sheet
  • the thickness of the carbon nanotube aggregate is, for example, 10 ⁇ m to 5000 ⁇ m, preferably 50 ⁇ m to 4000 ⁇ m, more preferably 100 ⁇ m to 3000 ⁇ m, and further preferably 300 ⁇ m to 2000 ⁇ m.
  • the thickness of the carbon nanotube aggregate is, for example, an average value of three points extracted at random within 0.2 mm or more from the end in the surface direction of the carbon nanotube aggregate layer.
  • the maximum static friction coefficient at 23 ° C. with respect to the glass surface of the carbon nanotube aggregate surface is preferably 1.0 or more.
  • the upper limit value of the maximum static friction coefficient is preferably 50. Within such a range, a carbon nanotube aggregate having excellent grip properties can be obtained.
  • the said adhesive structure with a large friction coefficient with respect to the glass surface can express strong grip property also to the mounted object (for example, semiconductor wafer) comprised from materials other than glass. A method for measuring the maximum static friction coefficient will be described later.
  • the carbon nanotube aggregate of the present invention can be applied to a conveyance fixture.
  • the transport fixture may be suitably used in a semiconductor element manufacturing process, an optical member manufacturing process, and the like.
  • the transport fixture is made of a material, an intermediate product, a product, etc. (specifically, a semiconductor material, a wafer, a chip) between processes in a semiconductor element manufacturing process or within a predetermined process. , Substrates, ceramic plates, films, etc.).
  • it can be used for transferring a glass substrate or the like between processes in manufacturing an optical member or within a predetermined process.
  • the carbon nanotube aggregate of the present invention has a non-oriented portion near the end in the length direction.
  • the aggregate of carbon nanotubes having a non-orientation part in the vicinity of the end in the length direction preferably has an orientation part, that is, a configuration in which a non-orientation part exists at the end of the orientation part.
  • the aggregate of carbon nanotubes having a non-oriented portion in the vicinity of the end in the length direction may have a non-oriented portion only on one side, or may have a non-oriented portion on both sides.
  • the aggregate of carbon nanotubes having a non-oriented portion near the end in the length direction has a non-oriented portion located in a place other than the vicinity of the end in addition to the non-oriented portion located near the end. Also good.
  • a placed object for example, a semiconductor material
  • Such an effect is considered to be obtained due to the fact that the network structure of the non-oriented portion has dissipative energy and that the actual contact area between the placed object and the carbon nanotube is increased by the network structure.
  • the thickness of the non-oriented portion located near the end is preferably 0.5 ⁇ m or more, more preferably 0.5 ⁇ m to 50 ⁇ m. More preferably, it is 0.5 ⁇ m to 20 ⁇ m, more preferably 0.5 ⁇ m to 15 ⁇ m, and particularly preferably 2 ⁇ m to 12 ⁇ m. If it is such a range, the carbon nanotube aggregate which can express the outstanding grip force can be obtained. Further, within the above range (that is, when the thickness is 50 ⁇ m or less), the thicker the non-oriented portion located near the end portion, the higher the grip force can be obtained.
  • the ratio of the thickness of the non-oriented portion located near the end is determined by the thickness of the carbon nanotube aggregate (the thickness of the aligned portion and the non-oriented portion). Is preferably 0.001% to 50%, more preferably 0.01% to 40%, still more preferably 0.05% to 30%, and particularly preferably. 0.1% to 20%. If it is such a range, the carbon nanotube aggregate which can express the outstanding grip force can be obtained.
  • the maximum static friction coefficient at 23 ° C. with respect to the glass surface of the surface on which the non-oriented portion is formed is preferably 1.0 or more.
  • it is 1.5 or more, more preferably 3.0 or more, and particularly preferably 5.0 or more.
  • it is preferably 100 or less, more preferably 50 or less, still more preferably 30 or less, and particularly preferably 20 or less.
  • the frictional force at 23 ° C. with respect to the glass surface of the surface on which the non-oriented portion is formed is preferably 0.5 N or more, more preferably It is 0.7N to 50N, more preferably 1.5N to 30N, and particularly preferably 3N to 20N.
  • the friction force can be measured by the following procedure. ⁇ Friction force measurement method> On the slide glass, the surface opposite to the measurement surface of the aggregate of carbon nanotubes (size: 9 mm ⁇ 9 mm) is fixed via an adhesive tape (polyimide adhesive tape) to produce an evaluation sample.
  • the evaluation sample is placed on another slide glass with the friction force measurement surface of the evaluation sample facing down, and a weight is placed on the evaluation sample so that a load of 55 g is applied to the carbon nanotube aggregate.
  • the evaluation sample is pulled in the horizontal direction with the weight placed thereon, and the frictional force is measured with a hanging scale (trade name “393-25” manufactured by CUSTOM).
  • a hanging scale (trade name “393-25” manufactured by CUSTOM).
  • a numerical value is adopted for a value of 0.05 kg or more for the hanging scale notation, and when it is less than 0.05 kg, it is evaluated as 0 kg and is defined as a frictional force.
  • the characteristics other than the matters described in the section A-1-1 are as described in the section A-1.
  • Carbon nanotube The carbon nanotube which comprises a carbon nanotube aggregate can take the below-mentioned embodiment (1st Embodiment, 2nd Embodiment), for example.
  • the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes have a plurality of layers, the distribution width of the number distribution of the carbon nanotubes is 10 or more, and the number of the layers The relative frequency of the mode of the distribution is 25% or less.
  • the aggregate of carbon nanotubes having such a configuration is excellent in adhesive strength.
  • the distribution width of the number distribution of carbon nanotubes is preferably 10 or more, more preferably 10 to 30 layers, still more preferably 10 to 25 layers, and particularly preferably. Is 10 to 20 layers.
  • the “distribution width” of the number distribution of carbon nanotubes refers to the difference between the maximum number and the minimum number of carbon nanotube layers.
  • the number of carbon nanotube layers and the number distribution of the carbon nanotubes may be measured by any appropriate apparatus. Preferably, it is measured by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). For example, at least 10, preferably 20 or more carbon nanotubes may be taken out from the aggregate of carbon nanotubes and measured by SEM or TEM to evaluate the number of layers and the number distribution of the layers.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the maximum number of carbon nanotube layers is preferably 5 to 30 layers, more preferably 10 to 30 layers, and even more preferably 15 to 30 layers. Particularly preferred are 15 to 25 layers.
  • the minimum number of carbon nanotube layers is preferably 1 to 10 layers, and more preferably 1 to 5 layers.
  • the relative frequency of the mode value of the number distribution of the carbon nanotubes is preferably 25% or less, more preferably 1% to 25%, and further preferably 5% to 25%. Yes, particularly preferably 10% to 25%, most preferably 15% to 25%.
  • the mode value of the number distribution of carbon nanotubes preferably exists in the number of layers 2 to 10 and more preferably in the number of layers 3 to 10.
  • the shape of the carbon nanotube it is sufficient that its cross section has any appropriate shape.
  • the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.
  • the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm.
  • the specific surface area and density of the carbon nanotubes can be set to any appropriate values.
  • the aggregate of carbon nanotubes includes a plurality of carbon nanotubes, the carbon nanotubes have a plurality of layers, and the mode value of the number distribution of the carbon nanotubes is present in the number of layers of 10 or less.
  • the relative frequency of the mode value is 30% or more.
  • the aggregate of carbon nanotubes having such a configuration is excellent in adhesive strength.
  • the distribution width of the number distribution of carbon nanotubes is preferably 9 or less, more preferably 1 to 9 layers, still more preferably 2 to 8 layers, and particularly preferably. Is 3 to 8 layers.
  • the maximum number of carbon nanotube layers is preferably 1 to 20 layers, more preferably 2 to 15 layers, and further preferably 3 to 10 layers.
  • the minimum number of carbon nanotube layers is preferably 1 to 10 layers, and more preferably 1 to 5 layers.
  • the relative frequency of the mode value of the number distribution of the carbon nanotubes is preferably 30% or more, more preferably 30% to 100%, and further preferably 30% to 90%. Particularly preferably 30% to 80%, most preferably 30% to 70%.
  • the mode value of the number distribution of carbon nanotubes is preferably present in the number of layers of 10 or less, more preferably in the number of layers from 1 to 10, and more preferably in the number of layers.
  • the number of layers is from 2 to 8 and particularly preferably from 2 to 6 layers.
  • the cross section may have any appropriate shape.
  • the cross section may be substantially circular, elliptical, n-gonal (n is an integer of 3 or more), and the like.
  • the diameter of the carbon nanotube is preferably 0.3 nm to 2000 nm, more preferably 1 nm to 1000 nm, and further preferably 2 nm to 500 nm.
  • the specific surface area and density of the carbon nanotubes can be set to any appropriate values.
  • a chemical layer is formed by growing a carbon nanotube by forming a catalyst layer on a substrate, supplying a carbon source in a state where the catalyst is activated by heat, plasma, or the like.
  • Examples thereof include a method of producing an aggregate of carbon nanotubes oriented substantially vertically from a base material by a phase growth method (Chemical Vapor Deposition: CVD method).
  • Arbitrary appropriate base materials can be employ
  • the material which has smoothness and the high temperature heat resistance which can endure manufacture of a carbon nanotube is mentioned.
  • examples of such materials include metal oxides such as quartz glass, zirconia, and alumina, metals such as silicon (silicon wafers), aluminum, copper, carbides such as silicon carbide, silicon nitride, aluminum nitride, and gallium nitride. And nitrides thereof.
  • any appropriate apparatus can be adopted as an apparatus for producing the carbon nanotube aggregate.
  • a thermal CVD apparatus as shown in FIG. 4, a hot wall type configured by surrounding a cylindrical reaction vessel with a resistance heating type electric tubular furnace, and the like can be mentioned.
  • a heat-resistant quartz tube is preferably used as the reaction vessel.
  • Any suitable catalyst can be used as a catalyst (catalyst layer material) that can be used in the production of the carbon nanotube aggregate.
  • metal catalysts such as iron, cobalt, nickel, gold, platinum, silver, copper, are mentioned.
  • an intermediate layer may be provided between the base material and the catalyst layer as necessary.
  • the material constituting the intermediate layer include metals and metal oxides.
  • the intermediate layer is composed of an alumina / hydrophilic membrane.
  • any appropriate method can be adopted as a method for producing the alumina / hydrophilic film.
  • it can be obtained by preparing a SiO 2 film on a substrate, evaporating Al, and then oxidizing it by raising the temperature to 450 ° C.
  • Al 2 O 3 interacts with the SiO 2 film hydrophilic, different Al 2 O 3 surface particle diameters than those deposited Al 2 O 3 directly formed.
  • Al is deposited and heated to 450 ° C. and oxidized without producing a hydrophilic film on the substrate, Al 2 O 3 surfaces with different particle diameters may not be formed easily. .
  • Al 2 O 3 surfaces having different particle diameters may not be easily formed.
  • the thickness of the catalyst layer that can be used in the production of the carbon nanotube aggregate is preferably 0.01 nm to 20 nm, more preferably 0.1 nm to 10 nm in order to form fine particles. By adjusting the thickness of the catalyst layer that can be used for the production of the carbon nanotube aggregate within the above range, a carbon nanotube aggregate having a non-oriented portion can be formed.
  • the amount of the catalyst layer that can be used for producing the carbon nanotube aggregate is preferably 50 ng / cm 2 to 3000 ng / cm 2 , more preferably 100 ng / cm 2 to 1500 ng / cm 2 , and particularly preferably 300 ng / cm 2. 2 to 1000 ng / cm 2 .
  • a carbon nanotube aggregate having a non-oriented portion can be formed.
  • Any appropriate method can be adopted as a method for forming the catalyst layer.
  • a method of depositing a metal catalyst by EB (electron beam), sputtering, or the like, a method of applying a suspension of metal catalyst fine particles on a substrate, and the like can be mentioned.
  • the catalyst layer formed by the above method can be atomized by a treatment such as heating to be used for producing a carbon nanotube aggregate.
  • the temperature of the heat treatment is preferably 400 ° C to 1200 ° C, more preferably 500 ° C to 1100 ° C, still more preferably 600 ° C to 1000 ° C, and particularly preferably 700 ° C to 900 ° C.
  • the heat treatment holding time is preferably 0 minutes to 180 minutes, more preferably 5 minutes to 150 minutes, further preferably 10 minutes to 120 minutes, and particularly preferably 15 minutes to 90 minutes. is there.
  • a carbon nanotube aggregate in which non-oriented portions are appropriately formed can be obtained by performing the heat treatment.
  • the average particle size of the equivalent circle diameter is preferably 1 nm to 300 nm, more preferably 3 nm to 100 nm, and still more preferably.
  • the thickness is 5 nm to 50 nm, and particularly preferably 10 nm to 30 nm.
  • an aggregate of carbon nanotubes in which non-oriented portions are appropriately formed can be obtained as long as the size of the catalyst fine particles.
  • any appropriate carbon source can be used as the carbon source that can be used for the production of the carbon nanotube aggregate.
  • hydrocarbons such as methane, ethylene, acetylene, and benzene
  • alcohols such as methanol and ethanol
  • the formation of the non-oriented portion can be controlled by the type of carbon source used.
  • the said non-orientation part is formed by using ethylene for a carbon source.
  • the carbon source is supplied as a mixed gas together with helium, hydrogen and / or water vapor.
  • the formation of the non-oriented portion can be controlled by the composition of the mixed gas.
  • the non-oriented portion can be formed by increasing the amount of hydrogen in the mixed gas.
  • the concentration of the carbon source (preferably ethylene) at 23 ° C. is preferably 2 vol% to 30 vol%, more preferably 2 vol% to 20 vol%.
  • the concentration of helium at 23 ° C. is preferably 15 vol% to 92 vol%, more preferably 30 vol% to 80 vol%.
  • the concentration of hydrogen in the mixed gas at 23 ° C. is preferably 5 vol% to 90 vol%, more preferably 20 vol% to 90 vol%.
  • the concentration of water vapor at 23 ° C. is preferably 0.02 vol% to 0.3 vol%, and more preferably 0.02 vol% to 0.15 vol%.
  • an aggregate of carbon nanotubes in which non-oriented portions are appropriately formed can be obtained.
  • the volume ratio (hydrogen / carbon source) of carbon source (preferably ethylene) and hydrogen at 23 ° C. is preferably 2 to 20, more preferably 4 to 10. If it is such a range, the carbon nanotube aggregate in which the non-orientation part was formed appropriately can be obtained.
  • the volume ratio (hydrogen / water vapor) of water vapor and hydrogen at 23 ° C. is preferably 100 to 2000, and more preferably 200 to 1500. If it is such a range, the carbon nanotube aggregate in which the non-orientation part was formed appropriately can be obtained.
  • Arbitrary appropriate temperature can be employ
  • the temperature is preferably 400 ° C to 1000 ° C, more preferably 500 ° C to 900 ° C, and further preferably 600 ° C to 800 ° C. More preferably, it is 700 ° C to 800 ° C, and particularly preferably 730 ° C to 780 ° C.
  • the formation of the non-oriented portion can be controlled by the manufacturing temperature.
  • a catalyst layer is formed on a substrate, a carbon source is supplied in a state where the catalyst is activated, a carbon nanotube is grown, and then the carbon source is supplied. Stop and maintain the carbon nanotubes at the reaction temperature in the presence of a carbon source.
  • formation of the said non-orientation part is controllable by the conditions of this reaction temperature maintenance process.
  • a catalyst layer is formed on a substrate, a carbon source is supplied in a state where the catalyst is activated, and carbon nanotubes are grown.
  • the carbon nanotubes may be compressed by applying a predetermined load in the thickness direction of the nanotubes.
  • an aggregate of carbon nanotubes (FIG. 3) composed only of non-oriented portions of carbon nanotubes can be obtained.
  • the load for example, a 1g / cm 2 ⁇ 10000g / cm 2, preferably, a 5g / cm 2 ⁇ 1000g / cm 2, more preferably 100g / cm 2 ⁇ 500g / cm 2.
  • the thickness of the carbon nanotube layer after compression ie, the aggregate of carbon nanotubes
  • the thickness of the carbon nanotube layer after compression is 10% to 90%, preferably 20% to 80%. More preferably, it is 30% to 60%.
  • the carbon nanotube aggregate of the present invention is obtained by collecting the carbon nanotube aggregate from the base material.
  • the aggregate of carbon nanotubes can be collected with the sheet shape formed on the substrate.
  • the sheet of the present invention is composed of the carbon nanotube aggregate.
  • seat of this invention is comprised only from a carbon nanotube aggregate.
  • the use of the sheet of the present invention is not particularly limited.
  • seat of this invention can be used suitably as an adhesive conveyance member in a conveying apparatus, for example.
  • the thickness of the carbon nanotube aggregate and the thickness of the non-oriented portion were measured by observing the cross section of the carbon nanotube aggregate with an SEM.
  • the standard deviation of the orientation degree of the carbon nanotube was obtained for each 500 nm-thick section by the method described in the section A, and the total thickness of the sections where the standard deviation was 40 ° or more was defined as the thickness of the non-oriented portion.
  • the maximum static friction coefficient of the carbon nanotube aggregate was measured by the following method. ⁇ Maximum static friction coefficient against glass surface> The friction force was measured by the following method, and the value obtained by dividing the friction force by the load was defined as the maximum static friction coefficient. (Friction force measurement method) On the slide glass, the surface opposite to the measurement surface of the aggregate of carbon nanotubes (size: 9 mm ⁇ 9 mm) was fixed via an adhesive tape (polyimide adhesive tape) to prepare an evaluation sample. Next, the evaluation sample is placed on another slide glass (size: 26 mm ⁇ 76 mm) with the friction force measurement surface of the evaluation sample facing down, and a weight is placed on the evaluation sample to form a carbon nanotube aggregate. The load was set to 55 g.
  • the evaluation sample was pulled in the horizontal direction with a weight (pulling speed: 100 mm / min), and the maximum load when the evaluation sample started to move was defined as a frictional force.
  • a hanging scale manufactured by CUSTOM, trade name “393-25” was used. A numerical value was adopted for a value of 0.05 kg or more when the suspended scale was represented, and when it was less than 0.05 kg, it was evaluated as 0 kg, and was defined as a frictional force.
  • the carbon nanotube aggregate was compressed by applying a load of 300 g, and the frictional force was measured as described above.
  • Example 1 Production of aggregate of carbon nanotubes 3922 ng / cm 2 on a silicon substrate (manufactured by VALQUA EFT Co., Ltd., thickness 700 ⁇ m) by a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics Co., Ltd.) An Al 2 O 3 thin film (degree of ultimate vacuum: 8.0 ⁇ 10 ⁇ 4 Pa, sputtering gas: Ar, gas pressure: 0.50 Pa) was formed.
  • an Fe thin film of 294 ng / cm 2 was further formed as a catalyst layer (sputtering gas: Ar, gas pressure: 0.1% by a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics). 75 Pa). Then, this base material was mounted in a 30 mm ⁇ quartz tube, and a helium / hydrogen (105/80 sccm) mixed gas maintained at a moisture content of 700 ppm was allowed to flow through the quartz tube for 30 minutes to replace the inside of the tube. Thereafter, the inside of the tube was heated to 765 ° C. using an electric tubular furnace and stabilized at 765 ° C.
  • a mixed gas of helium / hydrogen / ethylene (105/80/15 sccm, moisture content 700 ppm) was filled in the tube, and left for 60 minutes to grow carbon nanotubes on the substrate. Thereafter, the source gas was stopped, and the mixture was cooled while flowing a helium / hydrogen (105/80 sccm) mixed gas maintained at a moisture content of 700 ppm into the quartz tube.
  • a carbon nanotube aggregate having a thickness of 1100 ⁇ m was obtained.
  • the portion 1 ⁇ m above the silicon substrate is a non-oriented portion having a thickness of 4 ⁇ m (standard deviation of orientation degree: 40 ° to 67 °, average of standard deviation (sum of standard deviations of each section / section) Number (8 pieces)): 48 °).
  • the aggregate of carbon nanotubes could be peeled off from the silicon substrate into a sheet shape using tweezers.
  • the maximum static friction coefficient of the carbon nanotube aggregate on the silicon substrate side surface was 7.1.
  • Example 2 Production of carbon nanotube aggregate A carbon nanotube aggregate was obtained in the same manner as in Example 1 except that the growth time of carbon nanotubes was set to 32 minutes. The thickness of the obtained carbon nanotube aggregate was 550 ⁇ m. Further, the end portion on the silicon substrate side is a non-oriented portion having a thickness of 5 ⁇ m (standard deviation of orientation degree: 41 ° to 53 °, average of standard deviation (total of standard deviation of each section / number of sections (10)): 47 °). The aggregate of carbon nanotubes could be peeled off from the silicon substrate into a sheet shape using tweezers. Moreover, the maximum static friction coefficient of the carbon nanotube aggregate on the silicon substrate side surface was 9.3.
  • Example 3 Production of carbon nanotube aggregate A carbon nanotube aggregate was obtained in the same manner as in Example 1, except that the growth time of carbon nanotubes was 60 minutes.
  • the obtained carbon nanotube aggregate had a thickness of 350 ⁇ m.
  • the end portion on the silicon substrate side is a non-oriented portion having a thickness of 2 ⁇ m (standard deviation of orientation degree: 52 ° to 58 °, average of standard deviation (total of standard deviation of each section / number of sections (4)): 55 °).
  • the aggregate of carbon nanotubes could be peeled off from the silicon substrate into a sheet shape using tweezers. Further, the maximum coefficient of static friction of the carbon nanotube aggregate on the silicon substrate side surface was 3.1.
  • Example 4 Production of aggregate of carbon nanotubes Helium / hydrogen / ethylene (105/100/15 sccm, water content 700 ppm) mixed instead of helium / hydrogen / ethylene (105/80/15 sccm, water content 700 ppm) mixed gas
  • a carbon nanotube aggregate was obtained in the same manner as in Example 1 except that gas was used.
  • the obtained carbon nanotube aggregate had a thickness of 1000 ⁇ m.
  • the edge part on the opposite side to a silicon base material was a 0.5 micrometer-thick non-orientation part (standard deviation of orientation degree: 45 degrees).
  • the aggregate of carbon nanotubes could be peeled off from the silicon substrate into a sheet shape using tweezers.
  • the maximum static friction coefficient of the carbon nanotube aggregate on the surface opposite to the silicon substrate was 1.3.
  • Example 5 Production of carbon nanotube aggregate A carbon nanotube aggregate was obtained in the same manner as in Example 1 except that the amount of Fe thin film as the catalyst layer was changed from 294 ng / cm 2 to 725 ng / cm 2. It was. The obtained carbon nanotube aggregate had a thickness of 1000 ⁇ m. Further, the end portion on the silicon substrate side is a non-oriented portion having a thickness of 12 ⁇ m (standard deviation of orientation degree: 40 ° to 65 °, average of standard deviation (total of standard deviation of each section / number of sections (4)): 48 °). The aggregate of carbon nanotubes could be peeled off from the silicon substrate into a sheet shape using tweezers. The maximum coefficient of static friction of the carbon nanotube aggregate on the silicon substrate side surface was 13.
  • Example 6 Production of carbon nanotube aggregate After obtaining a carbon nanotube aggregate (thickness: 1100 ⁇ m) in the same manner as in Example 1, a load of 300 g was applied to the carbon nanotube aggregate (area: 0.81 cm 2 ). Was gradually compressed to compress the aggregate of carbon nanotubes.
  • the aggregate of carbon nanotubes thus obtained has a thickness of 600 ⁇ m, and the whole is a non-oriented portion (standard deviation of orientation degree: 40 ° to 73 °, average of standard deviation (total of standard deviation of each section) / Number of compartments (1200)): 56 °).
  • the aggregate of carbon nanotubes could be peeled off from the silicon substrate into a sheet shape using tweezers.
  • the maximum static friction coefficient of the carbon nanotube aggregate was 9.5.
  • an Fe thin film of 294 ng / cm 2 was further formed as a catalyst layer (sputtering gas: Ar, gas pressure: 0.1% by a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics). 75 Pa). Then, this base material was mounted in a 30 mm ⁇ quartz tube, and a mixed gas of helium / hydrogen (85/60 sccm) maintained at a moisture content of 600 ppm was allowed to flow in the quartz tube for 30 minutes to replace the inside of the tube. Thereafter, the inside of the tube was heated to 765 ° C. using an electric tubular furnace and stabilized at 765 ° C.
  • Example 5 Production of aggregate of carbon nanotubes 3922 ng / cm 2 on a silicon substrate (manufactured by VALQUA FT Co., Ltd., thickness 700 ⁇ m) by a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics Co., Ltd.) An Al 2 O 3 thin film (degree of ultimate vacuum: 8.0 ⁇ 10 ⁇ 4 Pa, sputtering gas: Ar, gas pressure: 0.50 Pa) was formed.
  • an Fe thin film of 725 ng / cm 2 was further formed on a catalyst layer (sputtering gas: Ar, gas pressure: 0.00%) using a sputtering apparatus (trade name “CFS-4ES” manufactured by Shibaura Mechatronics). 75 Pa). Then, this base material was mounted in a 30 mm ⁇ quartz tube, and a helium / hydrogen (105/80 sccm) mixed gas maintained at a moisture content of 750 ppm was allowed to flow through the quartz tube for 30 minutes to replace the inside of the tube. Thereafter, the inside of the tube was heated to 765 ° C. using an electric tubular furnace and stabilized at 765 ° C.
  • a mixed gas of helium / hydrogen / ethylene (105/80/15 sccm, water content 750 ppm) was filled into the tube, and left for 60 minutes to grow carbon nanotubes on the substrate. Thereafter, the source gas was stopped, and the mixture was cooled while flowing a helium / hydrogen (105/80 sccm) mixed gas maintained at a moisture content of 750 ppm into the quartz tube.
  • a carbon nanotube aggregate having a thickness of 1000 ⁇ m was obtained. This aggregate of carbon nanotubes had a non-oriented portion at the end portion on the silicon substrate side.
  • Example 6 The amount of Fe thin film as the catalyst layer was changed from 725 ng / cm 2 to 540 ng / cm 2 , and the water content of the helium / hydrogen (105/80 sccm) mixed gas and helium / hydrogen / ethylene (105/80/15 sccm) mixed gas A carbon nanotube aggregate was obtained in the same manner as in Example 5 except that the value was changed from 750 ppm to 500 ppm. The obtained carbon nanotube aggregate had a thickness of 800 ⁇ m. This aggregate of carbon nanotubes had a non-oriented portion at the end portion on the silicon substrate side.
  • Example 7 The amount of Fe thin film as the catalyst layer was changed from 725 ng / cm 2 to 540 ng / cm 2 , and helium / hydrogen (105/60 sccm) mixed gas was used instead of helium / hydrogen (105/80 sccm) mixed gas, and helium A carbon nanotube aggregate was prepared in the same manner as in Example 5 except that a mixed gas of helium / hydrogen / ethylene (105/60/15 sccm) was used instead of the mixed gas of hydrogen / hydrogen / ethylene (105/80/15 sccm). Obtained. The obtained carbon nanotube aggregate had a thickness of 1000 ⁇ m. This aggregate of carbon nanotubes had a non-oriented portion at the end opposite to the silicon substrate.
  • Example 8 The amount of Fe thin film as the catalyst layer was changed from 725 ng / cm 2 to 540 ng / cm 2 , and helium / hydrogen (105/100 sccm) mixed gas was used instead of helium / hydrogen (105/80 sccm) mixed gas, and helium A carbon nanotube aggregate was prepared in the same manner as in Example 5 except that a mixed gas of helium / hydrogen / ethylene (105/100/15 sccm) was used instead of the mixed gas of hydrogen / hydrogen / ethylene (105/80/15 sccm). Obtained. The obtained carbon nanotube aggregate had a thickness of 1000 ⁇ m. This aggregate of carbon nanotubes had a non-oriented portion at the end opposite to the silicon substrate.
  • Example 9 The amount of Fe thin film as the catalyst layer was changed from 725 ng / cm 2 to 540 ng / cm 2 and replaced with a helium / hydrogen / ethylene (105/80/15 sccm) mixed gas instead of helium / hydrogen / ethylene (105/100 / 5 sccm)
  • a carbon nanotube aggregate was obtained in the same manner as in Example 5 except that the mixed gas was used.
  • the obtained carbon nanotube aggregate had a thickness of 100 m.
  • This aggregate of carbon nanotubes had a non-oriented portion at the end opposite to the silicon substrate.
  • a carbon nanotube aggregate having a non-oriented portion at the end in the length direction of the carbon nanotube aggregate has a high maximum static friction coefficient.
  • Such an aggregate of carbon nanotubes can express a high grip force.
  • the carbon nanotube aggregates of Examples 5 to 9 could be peeled from the silicon base material into a sheet shape using tweezers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un agrégat de nanotubes de carbone capable de conserver une forme de feuille. Cet agrégat de nanotubes de carbone est configuré à partir d'une pluralité de nanotubes de carbone en une forme de feuille et a une partie non orientée des nanotubes de carbone. Dans un mode de réalisation, l'agrégat de nanotubes de carbone comprend en outre une partie orientée des nanotubes de carbone. Dans un mode de réalisation, la partie non orientée est présente au niveau d'une partie d'extrémité dans le sens de la longueur de l'agrégat de nanotubes de carbone.
PCT/JP2017/027492 2016-08-12 2017-07-28 Agrégat de nanotubes de carbone Ceased WO2018030182A1 (fr)

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EP17839255.1A EP3498669A4 (fr) 2016-08-12 2017-07-28 Agrégat de nanotubes de carbone
CN201780049407.5A CN109562945A (zh) 2016-08-12 2017-07-28 碳纳米管集合体
KR1020197003788A KR102477740B1 (ko) 2016-08-12 2017-07-28 카본 나노 튜브 집합체
US16/324,759 US20190177165A1 (en) 2016-08-12 2017-07-28 Carbon nanotube aggregate

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240260244A1 (en) * 2020-08-05 2024-08-01 Nitto Denko Corporation Laminate and electromagnetic wave absorber

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001351961A (ja) 2000-06-07 2001-12-21 Taiheiyo Cement Corp Ｓｉウェハ搬送治具及びその製造方法
JP2013138152A (ja) 2011-12-28 2013-07-11 Toshin Sangyo Co Ltd 搬送治具、搬送方法、および搬送治具材料
JP2013234115A (ja) * 2012-05-04 2013-11-21 Qinghua Univ カーボンナノチューブ構造体の製造方法
JP2013234116A (ja) * 2012-05-04 2013-11-21 Qinghua Univ カーボンナノチューブ構造体及びそれを利用した電界放出表示装置
JP2014234338A (ja) * 2013-06-05 2014-12-15 日立造船株式会社 カーボンナノチューブシートの製造方法及びカーボンナノチューブシート
JP2016046520A (ja) * 2014-08-21 2016-04-04 日東電工株式会社 半導体搬送部材および半導体載置部材
JP2017035743A (ja) * 2015-08-07 2017-02-16 日東電工株式会社 搬送装置
JP2017094412A (ja) * 2015-11-19 2017-06-01 日東電工株式会社 部品把持具

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001351961A (ja) 2000-06-07 2001-12-21 Taiheiyo Cement Corp Ｓｉウェハ搬送治具及びその製造方法
JP2013138152A (ja) 2011-12-28 2013-07-11 Toshin Sangyo Co Ltd 搬送治具、搬送方法、および搬送治具材料
JP2013234115A (ja) * 2012-05-04 2013-11-21 Qinghua Univ カーボンナノチューブ構造体の製造方法
JP2013234116A (ja) * 2012-05-04 2013-11-21 Qinghua Univ カーボンナノチューブ構造体及びそれを利用した電界放出表示装置
JP2014234338A (ja) * 2013-06-05 2014-12-15 日立造船株式会社 カーボンナノチューブシートの製造方法及びカーボンナノチューブシート
JP2016046520A (ja) * 2014-08-21 2016-04-04 日東電工株式会社 半導体搬送部材および半導体載置部材
JP2017035743A (ja) * 2015-08-07 2017-02-16 日東電工株式会社 搬送装置
JP2017094412A (ja) * 2015-11-19 2017-06-01 日東電工株式会社 部品把持具

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3498669A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240260244A1 (en) * 2020-08-05 2024-08-01 Nitto Denko Corporation Laminate and electromagnetic wave absorber

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