Fabrication of Hydrogen Sensors Using Graphenes Decorated Nanoparticles and Their Characteristics

J. Sensor Sci. & Tech. Vol. 21, No. 6, 2012 -425-

Journal of Sensor Science and Technology Vol. 21, No. 6 (2012) pp. 425-428

http://dx.doi.org/10.5369/JSST.2012.21.6.425 pISSN 1225-5475/eISSN 2093-7563

™Î‘⁄° ⁄√» ◊°… ‚› ˆ“æ≠« ¶¤˙ ◊ Ø∫

Ë≠Í , ^§ÕÛ+

Fabrication of Hydrogen Sensors Using

Graphenes Decorated Nanoparticles and Their Characteristics

Kang-San Kim and Gwiy-Sang Chung

Abstract

This paper presents the fabrication and characterization of graphene based hydrogen sensors. Graphene was synthesized by annealing process of Ni/3C-SiC thin films. Graphene was transferred onto oxidized Si substrates for fabrication of chemiresistive type hydrogen sensors. Au electrode on the graphene shows ohmic contact and the resistance is changed with hydrogen concentration. Nanoparticle catalysts of Pd and Pt were decorated. Response factor and response (recovery) time of hydrogen sensors based on the graphene are improved with catalysts. The response factors of pure graphene, Pt and Pd doped graphenes are 0.28, 0.6 and 1.26, respectively, at 50 ppm hydrogen concentration.

Keywords : Hydrogen sensor, Graphene, Pt, Pd, Nanoparticle

1. ≠ –

ˆ“° ˆ¬ 𪧨·™ ÷‰ ¯˜« ¯·Œ ¢§ª fiÌ

÷ˆ∏ , ^{¯‚Õ« Œ«ÒŒ} 4% ^{ÃÛ ∏Á“ ÊÏ°} 0.019 mJ ^{« ∑}

∫ Œ≠° ˆ° «ÿ ¤∫ ¯≠≠°μ ±‘ ¯flœ¬ ˆ“°∫«

؈∫ ßÆ° ŸÁ— ˆ“æ≠° ≥fl«Ì ÷Ÿ [1]. ^{◊Ø™ ÎŒ–}

« ÛÎ≠» ˆ“æ≠¬ ›”Í≠∞ª ‚›∏Œ œÁ °∫ Àˆ¶

ßÿ ‡ 400 …« ¬μ° ‰∏»Ÿ [2, 3]. ÃØ— ¬μ¬ °∫æ≠«

¿Î–fl° Η ¶—˙ Ù∫ ¸¬“ , ˝ÍÒΫ ı° Ó« ‹°

ª °¯Ÿ .

—Ì , ∫“¯⁄° ∞¢¸∏Œ ·’» ◊°…∫ ∑∫ ¸‚˙◊˙ ,

ÎÃÓ ◊ÆÌ 2 ˜¯ ∏∂« –∫ •È˚∏Œ Œÿ Û¬°≠ °∫

–⁄¶ Àˆ¶ ß— ∞˙Œ ¨∏«Ì ÷Ÿ [4]. ^{§ı˙ ◊ √∫√Ì}

Ø∫ª ÃÎœ© ŸÁ— ¸⁄“Á° ¿Î«Ì ÷Ì ÷Ÿ , ^√∫√Ì

ˆ“æ≠° ∏Ì«˙Ÿ [5]. ^◊Ø™ , ◊°…« ŸÁ— °∫–⁄Õ«

Ù∫ ›¿∫∏Œ Œÿ ا °∫¶ Àˆœ‚° Ó¡Ó ‹°Ã ÷Ÿ .

˚Û≠ , ◊°…ª ˆ“æ≠° ¿Îœ‚ ßÿ≠¬ ˆ“° Η ±√

μ ı°¶ ßÿ Pd ^◊ Pt Ó« À≈° ‰∏»Ÿ . ^{ÃØ— ›”È∫}

ˆ“° ΂«˙ª ÊÏ , ˆ“ ì« –ÿ° «ÿ PdH _x ^◊ PtH _x

¶ ¸∫œ© œ‘ˆ , ^{¸‚˙◊ ◊ ¸μμ} , ‚Ë˚ ¿¬ ◊ÆÌ ›”

À≈« ÛØà Ӫ fl˝√∞‘ »Ÿ [6, 7]. ◊°…« –∫ •È˚

« ÿÎ≠¶ ßÿ ™Î‘⁄« À≈∞˙à °Â ø≤˚Œ Õ∏Œ ∏ ŒŸ . ^÷Ÿ , ›”Í≠∞ ‚›« ˆ“æ≠° Pd ^◊ Pd ^{’›ª ÃÎ}

— ¨∏Èà ∏Ì«Ì ÷∏Á «— , ˆ“À≈Œ ¨∏«Ì ÷∏™ , Pd ^Õ Pt « Ò≥° ¸— ¨∏¬ πà ¯‡«ˆ  “Ÿ [8].

˚Û≠ , ª ¨∏°≠¬ •È˚ ‚Ûª ßÿ ™Îƒº¨ ‘⁄«

Pd ^Õ Pt ¶ ◊°… •È° ¢¢ ı¯œ© ¸‚≠–ƒ ˆ“æ≠¶ ¶

¤— ŸΩ° Ø∫ª Ò≥ –Æœ¥Ÿ .

2. « Ë

ª ¨∏°≠¬ ≠Í≠∑ ‚«° APCVD ^{¶ Îÿ} 1000 ^{…°≠ Ò}

§˙ 3C-SiC ⁄∑ª Ãæ·§∫Âfl∏Á ∫¤Õμ∏Œ Ni ^{¶ ‡} 200 ^{¨ ı¯œ¥Ÿ} . RTA (Rapid Thermal Annealing) ^{¯§ª Î}

ÿ ¬¬”μ : 35 ^… /s, ^{≠≥Æ√£} : 1 ^– , ^√¢”μ : 50 ^… /s ^{°≠ ◊°}

…ª ¸∫œ© SiO ₂ ‚«∏Œ ¸Á— ŸΩ° Au ^{¸ÿª ¸∫œ©}

¸‚≠–ƒ ˆ“æ≠¶ ¶¤œ¥Ÿ . Au ¸ÿà ı¯» ◊°…∫

Œ°¸– -10~10 V ^{¸ß°≠ ±¸˚Œ} Ohmic ^{¢’Ø∫à ™∏μ}

ÔÍΖ≥ ¸‚¯–Œ (School of Electrical Eng., University of Ulsan)

+

Corresponding author: [email protected]

(Received: Aug. 10, 2012, Revised : Sep. 18, 2012, Accepted: Oct. 15, 2012)

This is an Open Access article distributed under the terms of the Creative Commons

Attribution Non-Commercial License(http://creativecommons.org/licenses/by-

nc/3.0)which permits unrestricted non-commercial use, distribution, and

reproduction in any medium, provided the original work is properly cited.

Kang-San Kim

Gwiy-Sang Chung

|32|

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∏Á ˙◊∫ ‡ 358 ^{ÿ∏Œ™∏μŸ} . ˆ“° Η μ‚Ûª ßÿ

‡ 80 nm ^« Pd ^Õ Pt ¶ ™Î‘⁄ ¸¬Œ ◊°… •È° ı¯fl∏

Á Keithely probe station ^{ª ÃÎœ©} 10~50 ppm ^{¸ß« ˆ“}

Ûμ° ˚• æ≠« Àˆ Ø∫ª Ò≥œ¥Ÿ [9]. Fig. 1 ^{˙ ∞∫ ¯§}

√∫¤ª ÃÎœ© ˆ“« Ûμ¬ N ₂ ¶ ÒÆœ© ∂˝œÈ≠ Û¬

°≠ ¯§œ¥Ÿ .

3. ·˙ ◊ Ì˚

Fig. 2 ^¬ 50 ppm « ˆ“ Ûμ°≠ ◊°…˙ À≈° ˚• —÷‚

¿‰Ø∫ª ™∏Ω Õß . ^{¯ˆ ◊°…« ÊÏ} , ^{ˆ“° Η ›¿}

∫ ÷˙ˆ∏ , ˙◊« Ø≠° ¤‘ ™∏μŸ . ÃÕ∫ ◊°…˙ ˆ“

« ≠–˚ ›¿Ã ≠œˆ  Ωª ∏©ÿŸ . ^◊Ø™ , ^{À≈° ı¯»}

◊°…∫ ˆ“° Îÿ Ù∫ ˙◊Ø≠¶ ∏¥Ÿ . Pd ^{« ÊÏ} , Pt ^{° Ò}

ÿ Ù∫ ˙◊Ø≠Õ ¸• —÷‚¿‰ Ø∫ª ∏¥¬• , ^ÃÕ∫ Pt

° Η ˆ“« Îÿμ ∏Ÿ Pd ° Η ˆ“« Îÿμ° Ù‚ ßÆ Œ Õ∏Œ Á·»Ÿ [10].

Fig. 3 ∫ ◊°…˙ À≈° μŒ» ◊°… ˆ“æ≠« ¿‰Ëˆ¶

™∏Ω Õß . ¿‰Ëˆ¬ ˆ“Ûμ∞ æ≠‚¬ª £¢˚∏Œ À ˆ ÷∏Á ŸΩ« ƒ∏Œ §«œ¥Ÿ .

©‚≠ , R H2 ¬ ˆ“¶ ÷‘flª ß« ˙◊ , R air ^{∫ ˆ“¶ ÷‘œ} ˆ  “ª ß«  ‚˙◊ª ™∏ΩŸ . ◊°…« ¿‰Ëˆ¬ ˆ“Û μ° ˚Û ı°œ¥ˆ∏ , ^{Ø≠Æà ‡} 0.22 §μŒ ∑‘ ™∏μŸ .

—Ì , À≈° Áλ ◊°…« ¿‰Ëˆ¬ øœ Ûμ°≠ ◊°…°

Òÿ ı°œ¥Ì ؘ , Pd « ÊÏ ¿‰Ëˆ« Ø≠Æ∫ ‡ 1.01 ^Œ Pt ^« 0.26 ° Òÿ Ù∫ ˆ°¶ ∏¥Ÿ . ÃÕ∫ ◊°… ⁄ºŒ¬ ˆ

“Õ« ›¿Ã ≠œˆ  ∏Á À≈° «ÿ ˆ“›¿Ã ‚Û«˙Ω ª «Ã—Ÿ .

Fig. 4 ¬ ◊°…˙ À≈° μŒ» ◊°… ˆ“æ≠« (a) ^¿‰”

μÕ (b) ∏π”μ¶ ¢¢ ™∏Ω Õß . ˆ“Ûμ« ı°° ˚Û

¿‰√£∫ ı°œ¥∏Á 50 ppm ^{°≠ ¯ˆ ◊°…} , Pd ^{° μŒ»}

◊°… ◊ÆÌ Pt ° μŒ» ◊°…« ¿‰√£∫ ¢¢ 190, 140 ^◊

ÆÌ 158  Œ À≈¶ ÁΗ ÊÏ° Ø∫à ‚Û ª ÆŒœ¥∏Á

«— , ∏π√£°≠μ ØÁ— Ø∫ª ∏¥Ÿ . ◊°…« ÊÏ° ŸÁ

— °∫–⁄Èà Fermi ° ˆ« Û¬ –μ¶ Ø≠√∞¬ Õ∏Œ

∏Ì«˙Ÿ [11, 12]. ÃØ— ›¿∫ μ« §Æ∫ª °ˆ¬ ›È ,

¿∞ ¿‰”μÕ ∏π”μ¶ ∏ì• ÃØ— Ø∫∫ À≈« ‘⁄

©‚ ◊ –˜μ« Ø≠¶ Îÿ ‚Û√≥ ˆ ÷Ÿ .

Fig. 5 ¬ ¶¤» ˆ“æ≠« ˆ“Ûμ° ˚• √£˙ ˙◊« Ø

≠¶ Û¬°≠ ¯§— ◊°¡ÃŸ . ^{¯ˆ ◊°…˙} Pd ^{° μŒ» ◊}

°…°≠¬ ˆ“° ı°‘° ˚Û ˙◊à ±¸˚∏Œ Ø‘ª À ˆ

÷∏Á  ‚™« Ãø∫ ∏È  “Ÿ . ¯ˆ ◊°…° Òÿ À≈¶

ÁΗ ÊÏ , ¿‰√£˙ ∏π√£Ã ¸£‘ ™∏μ∏Á ›π˚Œ

«Ë°≠μ ¸• ¿‰ª ∏¥Ÿ . ^«— , Pt ° μŒ» ◊°… ™√ Ø Á— Ø∫ª ∏¥Ÿ . ‚∏° ∏Ì» ¨∏« ÊÏ° Pt ^{⁄∑ À≈¶}

ÃÎœ© Û¬°≠ 1% « ˆ“¶ Àˆ— ·˙° Òÿ ª ¨∏°≠

Áλ ™Î‘⁄ À≈« ÊÏ , ÛÎ˚∏Œ –∫ •È˚∏Œ Œÿ ˆ

ppm « ˙Ûμ ˆ“¶ Àˆ“ ˆ ÷Ÿ [13-15].

Fig. 1. Hydrogen sensor measurement system.

Response factor(%) =( ) ^§ 100 (1)

Fig. 2. One cycle response of sensors with catalysts at 50 ppm hydrogen concentration.

R H2 - R air

R air

Fig. 3. Response factors of the sensors of graphene and catalysts

decorated graphene with hydrogen concentrations.

Fabrication of Hydrogen Sensors Using Graphenes Decorated Nanoparticles and Their Characteristics |33|

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4. · –

ª ¨∏¬ Ni ^˛˙ SiC « ≠≥ƶ Îÿ ¸∫» ◊°… ‚› ¸‚

˙◊ƒ ˆ“æ≠ ¶¤˙ ◊ Ø∫° ¸— Õß . ^¸Á¯§˙ Au ^¸

ÿ ¸∫∏Œ ◊°… ‚› ˆ“æ≠¶ ¶¤fl∏Á ™Î‘⁄ Pd ^Õ Pt

¶ À≈Œ ÁÎœ© Ø∫ª Ò≥ –Æœ¥Ÿ . ^{◊°… ⁄ºŒ ˆ“}

Àˆ° °…flˆ∏ , ˆ“ì˙« ‡— ›¿∏Œ ∑∫ ¿‰Ëˆ ◊

›¿ , ∏π√£ª ∏¥∏™ À≈¶ ÁÎœ© Ø∫ª ‚Û√≥ ˆ ÷

˙Ÿ . Pd ^{« ÊÏ} , Pt ° Òÿ ˆ“« Îÿμ° Ù‚ ßÆ° Ù∫ ¿

‰Ëˆ ◊ ™∫ ›¿ , ^{∏π√£ª ∏¥Ÿ} . ™Î‘⁄ ©‚« ∂˝°

˚Û Ø∫∫ ‚Û… Õ∏Œ ª ¨∏°≠ ¶¤» ◊°… ‚› ˆ“

æ≠¬ Û¬°≠ ˆ“« Àˆ° °…œ© ˙Ûμ« ˆ“ ◊ VOC

æ≠° ¿Îà °…“ Õ∏Œ ‚λŸ .

Á« ¤

à ¨∏∫ ≥∞˙–‚˙ŒÕ —π¨∏Á‹« ˆ™ı≈Œ¬Á∫Á

˜˙ fl“‚˜ª« Í–¨¯ø‚˙≥fl Á˜∏Œ ˆ‡«¥¿œŸ .

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Ë ≠ Í (Kang-San Kim)

U 2012 ^‚ 3 ˘ ÔÍΖ≥ ¸‚¯–Œ ⁄Á

˙§ π˜

UˆÁ ÔÍΖ≥ ¸‚¯–Œ BK ^¨∏¯

U÷¸… –fl : Sensor, Graphene, SiC- MEMS

§ Õ Û (Gwiy-Sang Chung)

U 1992 ^‚ 3 ^˘ TUT ( ^¯–⁄Á )

U 2004 ^‚ 2 ^˘ UC Berkeley ^¨∏≥ˆ

U 2009 ^‚ 8 ^˘ Stanford Univ. ^ÊÆ≥ˆ

UˆÁ ÔÍΖ≥ ¸‚¯–Œ ≥ˆ U÷¸… –fl : Wireless Sensor Nodes,

Energy Harvesting, Graphene