US20030227958A1 - Nanotube, nano thermometer and method for producing the same - Google Patents

Nanotube, nano thermometer and method for producing the same Download PDF

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Publication number
US20030227958A1
US20030227958A1 US10/357,452 US35745203A US2003227958A1 US 20030227958 A1 US20030227958 A1 US 20030227958A1 US 35745203 A US35745203 A US 35745203A US 2003227958 A1 US2003227958 A1 US 2003227958A1
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temperature
nano thermometer
producing
powder
nano
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Yoshio Bando
Yihua Gao
Tadao Sato
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National Institute for Materials Science
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National Institute for Materials Science
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Assigned to NATIONAL INSTITUTE FOR MATERIALS SCIENCE reassignment NATIONAL INSTITUTE FOR MATERIALS SCIENCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BANDO, YOSHIO, GAO, YIHUA, SATO, TADAO
Publication of US20030227958A1 publication Critical patent/US20030227958A1/en
Priority to US11/230,510 priority Critical patent/US7291299B2/en
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K5/00—Measuring temperature based on the expansion or contraction of a material
    • G01K5/02—Measuring temperature based on the expansion or contraction of a material the material being a liquid
    • G01K5/04—Details
    • G01K5/08—Capillary tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/762—Nanowire or quantum wire, i.e. axially elongated structure having two dimensions of 100 nm or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/811—Of specified metal oxide composition, e.g. conducting or semiconducting compositions such as ITO, ZnOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
    • Y10S977/833—Thermal property of nanomaterial, e.g. thermally conducting/insulating or exhibiting peltier or seebeck effect
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/902—Specified use of nanostructure
    • Y10S977/932—Specified use of nanostructure for electronic or optoelectronic application
    • Y10S977/953—Detector using nanostructure
    • Y10S977/955—Of thermal property

Definitions

  • the present invention relates a nanotube, a nano thermometer and a method for producing the same. More particularly, the present invention relates to a nanotube, and novel nano thermometer using the nanotube, which can use for temperature measurement of a wide temperature range, in a micrometer size environment, and a method for producing the same.
  • CNTs carbon nanotubes
  • they can serve as field-effect devices, probe-tips for scanning probe microscope, superconducting material, high-sensitivity microbalances, structural materials, tiny tweezers for nanoscale manipulation, gas detectors and hydrogen energy storage devices etc.
  • thermometers designed for a macroscopic environment are no longer appropriate for a micrometer-size environment, and a nano thermometer, which can perform temperature measurement of micrometer size environment, is needed.
  • thermometer had the comparatively narrow temperature range which can be measured, and some thermometers needed to be prepared for every measurement temperature when a wide range temperature was measured.
  • the object is to provide a solution to the above-mentioned problems of the conventional thermometer, and to provide a novel nano thermometer, which enables temperature measurement of a wide temperature range in a micrometer size environment, and a method for producing the same.
  • FIG. 1( a ) shows the morphology of a wire indicated by the arrow
  • (b) shows the morphology of that the wire is wrapped by a thin layer on its round tip and body
  • (c) shows the HRTEM image of the thin wrapping layer
  • (d) shows an EDS spectrum from the region in (c).
  • FIG. 2 shows the morphologies of the Ga tip when the temperature increases from 18° C. (a), via 58° C. (b) and 294° C. (c), to 490° C. (d), as well as the morphologies when the temperature decreases from 490° C. (d), via 330° C. (e), 170° C. (f) and 45° C. (g), to 22° C. (h).
  • FIG. 3 shows the curves of height of the Ga tip-level vs temperature.
  • the present invention firstly provides, as a means to solve the above-mentioned problems, a nano thermometer, comprising a carbon nanotube filled with a continuous columnar gallium, which enables measurement of environmental temperature by length change of the columnar gallium.
  • the present invention secondly provides a nano thermometer, having length of 1-10 ⁇ m and diameters of 40-150 nm.
  • the invention thirdly provides a nano thermometer, which enables measurement of the temperature of the range of at least 50 to 500° C.
  • the present invention fourthly provides a nano thermometer, whose error is within 0.25° C.
  • the present invention fifthly provides a nanotube, comprising a carbon nanotube filled with a columnar gallium.
  • the present invention sixthly provide a method for producing a nano thermometer said method comprising mixing Ga 2 O 3 powder and carbon powder uniformly, performing heat treatment for this mixed powder at a temperature of 966° C. or more under an inert gas flow to vaporize, and making a reaction at a temperature of 835° C. or less.
  • the present invention seventhly provides a method for producing a nano thermometer, wherein a weight ratio of Ga 2 O 3 powder to carbon powder is 7.8:1.
  • the present invention eighthly provides a method for producing a nano thermometer, wherein carbon powder is an amorphous active carbon.
  • the present—invention ninthly provides a method for producing a nano thermometer, wherein inert gas is nitrogen gas, and tenthly provides a method for producing a nano thermometer, wherein heat treatment is performed using a vertical radio-frequency furnace. Also, the present invention eleventhly provides a method for producing a nano thermometer, wherein heat treatment is performed for 1 hour or more at a temperature of 1300 to 1400° C.
  • the present inventions provide a nano thermometer which can also be considered as novel potential application of a carbon nanotube (CNT). That is, the nanotube of the present invention comprising a carbon nanotube filled with a columnar gallium (Ga).
  • CNT carbon nanotube
  • Ga columnar gallium
  • the nano thermometer of the present invention comprising a CNT filled with a continuous columnar Ga, which enables measurement of environmental temperature by length change of the columnar Ga.
  • This potential application is based on the expansion characteristic of Ga in the inside of a CNT.
  • Ga has the form of as a continuous column.
  • the reason why Ga rather than another metal is chosen as the filling material is that Ga has one of the longest liquid ranges of any metal, i.e. 29.78-2,403° C., and has a low vapor pressure even at high temperatures, which makes it suitable for use in a wide-temperature-range thermometer. Therefore, the nano thermometer of the present invention has a potential wide measuring range due to the wide liquid range of Ga, 29.78 to 2,403° C., which is much wider than that of Hg, ⁇ 38.87 to 356.58° C.
  • thermometer the length of the columnar Ga increases linearly with increasing temperature in the temperature range of 50 to 500° C. Therefore, with the nano thermometer of the present invention, environmental temperature can be measured from the length of Ga simpler and correctly in the temperature range of 50 to 500° C.
  • the present nano thermometer even more surprising, can realize a very highly precise nano thermometer within 0.25° C. of errors.
  • the nano thermometer of the present invention uses the detailed structure of a CNT, the very small thermometer of a micrometer-size is realized.
  • the nano thermometer having length of 1-10 ⁇ m and diameters of 40-150 nm is realized.
  • Ga can be made to extend up to about 8 mm in CNT.
  • the nano thermometer of the present invention can play an important role in various researches involving temperature measurement of a wide temperature range in micrometer environment.
  • the nano thermometer of the present invention is producible by a method of present invention as follows. That is, in the method of the present invention, it is made to manufacture a nano thermometer by mixing Ga 2 O 3 powder and carbon powder uniformly, performing heat treatment for this mixed powder at a temperature of 966° C. or more under an inert gas flow to vaporize, and making a reaction at a temperature of 835° C. or less.
  • carbon powder can be used as raw material of the CNT part which constitutes a nano thermometer.
  • carbon powder carbon powder of comparatively high purity, for example 90% or more of purity, can be used.
  • Ga 2 O 3 powder can be used as raw material of the columnar Ga filling in the CNT.
  • a weight ratio of Ga 2 O 3 powder to carbon powder can be adjusted in the range of about 7:1 to 8:1, and is 7.8:1 more preferably.
  • Ga 2 O 3 powder and carbon powder are mixed uniformly, and are performed heat treatment at a temperature of 966° C. or more under an inert gas flow.
  • the mixed powder of Ga 2 O 3 and carbon is vaporizable at a temperature of 966° C. or more, it is more desirable that heat treatment is performed at the temperature range from 1200 to 1400° C.
  • an inert gas is desirable nitrogen gas.
  • the vapors are carried by the inert gas flow, and they can react at the temperature of 835° C. or less and are deposited.
  • a vertical radio-frequency furnace can be used in the method of the present invention. If a susceptor of the vertical radio-frequency furnace has one bottom inlet pipe and one top outlet pipe of the inert gas flow, the nano thermometer of the present invention can be obtained on the inner surface of the top outlet pipe as depositions, for example.
  • heat treatment can be performed at a temperature range from 1200 to 1400° C. as above-mentioned. More specifically, a heat treatment of 1 hour or more at the temperature from 1300 to 1400° C. can be made as a rough standard.
  • the nano thermometer was produced using the vertical radio-frequency furnace as described by the reference; Golberg, G. et al. Large-scale synthesis and HRTEM analysis of single-walled B- and N-doped carbon nanotube bundles. Carbon 38, 2017-2027 (2000).
  • the reactant was a homogenous mixed powder of Ga 2 O 3 and pure amorphous active carbon (AAC) in the weight ratio 7.8:1.
  • the graphite susceptor of the vertical radio-frequency furnace had one bottom inlet pipe and one top outlet pipe made of 99.99% purity graphite. Pure N 2 gas flow was introduced into the furnace. Heat treatment at 1,360° C. for 2 hours was performed for the reactant. After the heat treatment, the reactant in the graphite crucible disappeared, while some materials were found to have deposited on the inner surface of the top outlet graphite pipe. In the deposition zone, the temperature was measured to be ⁇ 800° C.
  • FIG. 1( a ) shows several 1-dimensional (1D) nanoscale wires of the deposited materials, which have lengths of 1-10 ⁇ m and diameters of 40-150 nm. The bar at the lower right corner corresponds to 1 ⁇ m. The wire indicated by the arrow was analyzed carefully.
  • the HRTEM image in FIG. 1( c ) shows that this thin layer is carbon.
  • FIG. 1( d ) an EDS spectrum from the region in (c).
  • the horizontal axis is Energy axis, while the vertical is Intensity in arbitrary unit.
  • the peaks of C-K ⁇ (0.28 keV), Ga-L ⁇ (1.10 keV), Ga-K ⁇ (9.24 keV) and Ga-K ⁇ (10.26 keV) are shown, the Cu peak was originated from the Cu TEM grid. That is, it shows that the wire contains Ga and C.
  • the—indicated wire is a CNT filled with Ga. From the left to the right of the CNT shown in (a), there are round tips, a long columnar Ga, a hollow space beside the arrowhead, a short columnar Ga and another hollow space. In (b), the length and outer diameter d 0 of the CNT are 9,180 nm and 85 nm, while the length L 0 and diameter d 1 of the longer columnar Ga are 7,560 nm and 75 nm, respectively. The round tip keeps its shape and size when the temperature changes.
  • the transmission electron microscope (TEM) specimen of the deposited materials was heated in the microscope using a Gatan heating holder and its twin heating system (Hot Stage Powder Supply, Model 628-0500).
  • the position of the Ga tip-level of the longer columnar Ga vs temperature was investigated in the range 18-500° C.
  • the Ga tip-level rises, as shown in FIGS. 2 ( a ), ( b ), ( c ) and ( d ).
  • the Ga tip-level goes down when the temperature decreases., as shown in FIGS. 2 ( e ), ( f ), ( g ) and ( h ).
  • the Ga tip-level goes up when'the temperature increases, while it goes down when the temperature decreases.
  • the bar in (a) corresponds to 85 nm. If the Ga tip-level at 58° C. is set as the reference zero point, the height of the Ga tip-level vs temperature can be plotted as shown in FIG. 3, where the lines which connect a black circles and a black triangles correspond to the increase process and reduction process of temperature, respectively. Moreover, when the temperature was changed from 20° C. to 500° C., the changes of the complete length and the inner-diameter of the CNT were measured and estimated to be ⁇ 1% due to the very small linear expansion coefficient of graphite ( ⁇ 1 ⁇ 10 ⁇ 6 /° C. along a axis in the range of 20-500° C.). Therefore, it is believed that the influence of the expansion of the CNT on the Ga tip-level position can be neglected and the height vs temperature is dominated by the volumetric change of the longer columnar Ga related to the environment temperature.
  • the coefficients b and c of Ga can be regarded as zero in the range 50-500° C.
  • the height of the Ga tip-level is reproducible and linearly changes in the range 50-500° C.
  • the characteristic in the range 20-50° C. is complicated and may be related to a liquefaction (or solidification) process when increasing (or decreasing) the temperature.
  • the CNT filled with along continuous columnar Ga can be used as a thermometer in the range of at least 50-500° C.
  • the height of the Ga tip-level is determined by
  • v 0 is the volume of a continuous columnar Ga at temperature t 0
  • ⁇ H is the difference between the heights of the Ga tip-level at temperatures t and t 0
  • the columnar Ga should have a large volume v 0 and a small diameter d 1 .
  • the nano thermometer of the present invention can be used for the measurement in a micrometer-size environment.
  • many researches have stepped into a size of at least micrometer. Therefore, the four kinds of thermometers designed for a macroscopic environment are no longer appropriate for a micrometer-size environment.
  • the nano thermometer of the present invention could, play an important role in various researches involving a temperature measurement of micrometer-size environment.
  • the present kind of nano thermometer filled with Ga has a potential wide measuring range due to the wide liquid range (29.78-2,403° C.) of Ga, which is much wider than that ( ⁇ 38.87-356.58° C.) of Hg.
  • the method for producing the CNTs filled with a long columnar Ga belongs to the second approach.
  • the growth of the Ga filling CNTs may involve two chemical reactions. At a temperature above 966° C., Ga 2 O and CO vapours can be generated by the reaction;
  • Ga 2 O 3 (solid) 2C(solid) ⁇ Ga 2 O(vapour)+2CO(vapour),
  • n ( m C ⁇ Ga d 1 2 )/[2 m Ga ⁇ C ( d 0 2 ⁇ d 1 2 )] (3)
  • n in estimated to be ⁇ 1.
  • a series of calculations on the change of Gibbs energy for the VV reaction at n ⁇ 1 illustrate that it can occur only at a temperature below 835° C., which is consistent with our experiment that the Ga filling CNTs were obtained in the low temperature zone ( ⁇ 800° C.).
  • the present invention provides novel nano thermometer, which can use for temperature measurement of a wide: temperature range, in a micrometer size environment, and a method for producing the same.

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JP2002067661A JP3686941B2 (ja) 2002-02-04 2002-02-04 ナノ温度計およびその製造方法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006082226A1 (de) 2005-02-03 2006-08-10 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Partikel zur ermittlung der lokalen temperatur

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JP3924616B2 (ja) 2003-06-30 2007-06-06 独立行政法人物質・材料研究機構 微小サイズの温度感知素子を用いる温度計測方法
JP2005306663A (ja) * 2004-04-21 2005-11-04 National Institute For Materials Science シリカナノチューブの製造方法とナノサイズ領域の微小温度計
JP2006001811A (ja) * 2004-06-18 2006-01-05 National Institute For Materials Science 炭素膜で被覆された酸化ガリウムナノケーブル及びその製造方法
WO2006003861A1 (ja) * 2004-06-30 2006-01-12 Japan Science And Technology Agency ナノジェット噴出方法、及びナノジェット機構
JP4571452B2 (ja) * 2004-07-06 2010-10-27 日本電信電話株式会社 超伝導三端子素子の製造方法
JP2007101474A (ja) * 2005-10-07 2007-04-19 National Institute For Materials Science ナノメートルサイズの微小温度スイッチ及びその製造方法
JP2007101503A (ja) * 2005-10-07 2007-04-19 National Institute For Materials Science ナノメートルサイズの微小温度計及びその製造方法
JP5069860B2 (ja) * 2006-01-31 2012-11-07 株式会社カネカ グラファイトフィルム
WO2008127776A1 (en) * 2007-02-14 2008-10-23 The Regents Of The University Of California A method to determine thermal profiles of nanoscale circuitry
US7780345B2 (en) * 2007-12-19 2010-08-24 Motorola, Inc. Method and apparatus for a temperature sensor for measuring peak temperatures
US9274008B2 (en) 2012-11-28 2016-03-01 Washington University Nanothermometer, methods and uses therefor
USD789809S1 (en) * 2015-12-22 2017-06-20 Shanghai Wener Information Technology Co., Ltd. Tumor cell thermometer
CN107727263A (zh) * 2017-10-19 2018-02-23 华为技术有限公司 热电偶和温度传感器
CN109811399B (zh) * 2019-01-25 2020-10-27 东南大学 一种尺寸可控Ga2O3纳米管的制备方法

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US20020055010A1 (en) * 1999-06-14 2002-05-09 Yufei Gao Carbon nanotubes on a substrate and method of making

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US1793303A (en) * 1925-01-28 1931-02-17 Gen Electric Temperature-responsive device
US5457343A (en) * 1992-12-22 1995-10-10 Nec Corporation Carbon nanotubule enclosing a foreign material
US6153299A (en) * 1995-09-28 2000-11-28 Alliedsignal Inc. Colored articles and compositions and methods for their fabrication
US20020014182A1 (en) * 1998-05-22 2002-02-07 Tapesh Yadav Nanostructured fillers and carriers
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006082226A1 (de) 2005-02-03 2006-08-10 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Partikel zur ermittlung der lokalen temperatur
US20080159960A1 (en) * 2005-02-03 2008-07-03 Rudiger Klingeler Particles for Determining the Local Temperature

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CN1259554C (zh) 2006-06-14
US20060013280A1 (en) 2006-01-19
US7291299B2 (en) 2007-11-06
JP2003227762A (ja) 2003-08-15
DE60316056T2 (de) 2008-06-05
EP1335192A1 (de) 2003-08-13
CN1442678A (zh) 2003-09-17
DE60316056D1 (de) 2007-10-18
EP1335192B1 (de) 2007-09-05

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