DC CVD

Development of DC pulse plasma CVD system with minimum

chamber volume and control of substrate temperature

1185071

28 2 15

1 p1

1.1

2 (Diamond-Like Carbon: DLC) p2

2.1 DLC

2.2 DLC

2.3 DLC

2.3.1 FCVA(Filtered Cathodic Vaccum Arc)

2.3.2 CVD(Chemical Vapor Deposition)

2.4 DLC

3 CVD p9

3.1 CVD

3.2 CVD

3.3 DC

3.4

3.5

3.6

3.7

4 DC DLC p21

4.1 CO DLC

4.1.1

4.1.2 DC

4.1.3

4.2

5 p28

1

1

1.1

Diamond-Like Carbon: DLC

CD

DLC

2

CVD DLC

DLC

tetrahedral amorphous

carbon: ta-C80 GPa 3 g/cm3

3.52 g/cm3 ta-C

Filtered Cathodic Vaccum Arc: FCVA

CVD

DLC DLC CVD

DLCC2H2 C6H6 C H

50 atm%

Konishi [1] CVD

DLC 6 % DLC 2

CVD

(CO) DLC

[2]CO DLC 15 GPa

4 atm% 20 atm%

CVD CVD

DLC

CVD

CVD

CO CVD ta-C

2

2 (Diamond-Like Carbon)

DLC CVD ta-

C

2.1 DLC

Diamond-Like Carbon: DLC

sp3

sp2

DLC

sp3 sp2

Amorphous-CarbonDLC

DLC 2.1 [3]DLC

2.1 [3]

2.1 DLC 2.2DLC

DLC

DLC

DLC

DLC

(g/cm3) 2.26 1.52.5 3.52

(HV) 100 10005000 800010000

(cm) 410-3 1071014 10131016

2.15 22.4 2.42

(eV) - 12 5.5

(GPa) - 100500 1150

(W/cmK) 0.42.1 0.2 620

() 600 300400 600

3

2.1 DLC [3]

2.2 DLC [3]

2.2 DLC

2.2 2.3 DLC[4] 2.2 sp3

DLC sp3

()ta-C(Tetrahedral amorphous Carbon) sp3 ()ta-

C:H(Hydrogenated Tetrahedral amorphous Carbon)sp3 sp2

()a-C(Amorphous Carbon) sp3 sp2 ()a-

C:H(Hydrogenated Amorphous Carbon) sp2

()GLC(Graphite Like Carbon) sp2()PLC(Polymer

Like Carbon) DLCPLC(1.4 g/cm3)

DLC

PET

()

4

0.59 GPa[4] 70 %

()

2.2 DLC [4]

2.3 DLC [4]

DLC

sp3sp2sp3

sp2

2.3 DLC

DLC

0

10

20

30

40

50

60

70

80

90

100

0.1 1 10 100

sp3

[

H [atm]

sp

3

[]

H

[atm]

ta-C 50sp390 H5

ta-C:H 50sp3100 5H50

a-C H5

a-C:H 5H50

GLC 0sp320 (0H5)

PLC - (50H70) sp3205H

- (70H)

20sp350

5

Physical Vapor DepositionPVDChemical Vapor DepositionCVD

PVD

CVD

PVD DLC

CVD

DLCElectron cyclotron Resonance: ECR

Radio Frequency: RF CVD CVD

sp3 ta-C

Filtered Cathodic Vaccum Arc: FCVA

CVD

2.3.1 FCVAFiltered Cathodic Vaccum Arc

m

DLC

FCVA

m

[5] 2.3

2.3.2 CVDChemical Vapor Deposition

Chemical Vapor Deposition: CVD

CVD CVD CVD CVD [6] 2.4

RF 13.56MHzMW 2.45GHz

CVD150300

[7-8]DLC

CH4 C2H2

6

CVD DLC

CVD DLC

a-C:H

sp3

5atm%ta-C 2590 GPa

3.52.6g/cm3[4]sp3 550atm% ta-C:H

935GPa 2.62.0g/cm3

CVD a-C:H 1025GPa 2.0

1.4g/cm3

2.3 FCVA[5]

Vaccum arc supply

v

vv

+

-

++

+

+

+

++

+ +

--

--

-

-

-

+

+ +

+

+

+

+

+

+

+

+ +

+

+

+

+ Su

bst

rate

Striker

Filter field

Focusing

magnetic field

Optical viewport

Substrate bias

7

2.4 CVD[6]

2.4 DLC

DLCRobertson

2.5

sp3 -

100 V sp38[9]

DLC

-100V sp3[10]

FCVA(Arc Ion Plating: AIP)100

eV sp3 9 DLC

CVD

CVD 100 eV

200300 eV [11]

sp3

700 1000DLC 500

FCVA

200 CVD

Konishi[1] CVDDLC

26% 23%250 DLC

2

(13.56 MHz)

+ +--

8

2.5 [8]

ta-C FCVA

ta-C

CVD a-C:H

CVD ta-C DLC

CVD ta-CDLC

sp3

DLC CO RF

CVD DLC CO DLC 15 GPa

4 atm% 20 atm%CO

DLC

RF CVD

CVD

CVD CO CVD ta-

C

relaxationpenetration

direct

9

3 CVD

CVD

CVD DC

3.1 CVD

3.1 CVD

3.2 CVD

3.2

3.2 CVD

3.1 CVD

DC

RF

10

3.2 CVD

3.2 CVD

CVD 3.3

1.6 L RF CVD[2] 1/17

CVD

4

120 mm 3.4

CVD (90 mm)CVD

2 mm

3.5

DC

RF

11

3.3 CVD

3.4 CVD

80 mm

160 mm

CVD90 mm)

12

3.5

Ar 10 Pa

V-130-5

3.6 400400

15 250 W 400

60 W 1 400

2 100

3.6

3.3 DC

DC

[12-13]DC

100 200

100

200

300

0

100

200

300

400

500

0

Po

wer

(W

)

Ele

ctro

de

tem

per

atu

re (

)

Time (min)

Ar 10 Pa

13

[14] 3.7 P 2

d V R

DC

Vb

Vd RVb=Vd-RId

Vd R 3.8 Id-Vd Id-Vd

3.7 DC

3.8 DC (Id-Vd)

Vd R

dP

Vb

Id

Vd

Id

Vd-RId

Id

14

3.9DCAr

(MFC) Ar 100 sccm

(TMP)(RP)

2.666 kPaMKS

4 (SUS304)

10 k15

k100 k200 k1 M 1 k

+1 kDC TMK1.0-50

PA500-0.1A(KENWOOD)

(PC700: sanwa)PC Link 7: sanwa

Ar 510

152050100150 Pa 0

0 1 1 5

Ar 3.10

3.9 Ar DC

1k

10 k, 15 k, 100 k,

200 k or 1 M

TMP RP

MFC

Ar

V1 V2 0~-1k V

PC

15

3.10 CVD DC Ar(50 Pa)

3.4

3.11 1 M 100 k 5 Pa

10-4 mA 10-1 mA-700 V

0.1 mA

0.2 mA 1 mA

1 mA-940 V 0.2 mA 1 mA

1 2

100 V

3.11 5 Pa

(a)1 M(b)100 k

3.12 1 M200 k10 k 20 Pa

10-3 mA 10-1 mA-320-300 V

10-4 10-3 10-2 10-1 1000

200

400

600

800

1000(a)1 M

1st2nd3rd4th5th

10-3 10-2 10-1 100 1010

200

400

600

800

1000

Current (mA)

(b)100 k

Vo

ltag

e (V

)

1st2nd3rd4th5th

16

0.15 mA 10 mA-480 V

1 M5 Pa

3.12 20 Pa

(a)1 M(b)200 k(c)10 k

3.13 150 Pa 10-2 mA 101 mA -300 V

-220 V 10 mA

100 mA-350 V 1

3.13 150 Pa

(a)1 M(b)200 k(c)10 k

10-3 10-2 10-1 1000

100

200

300

400

500(b)200 k

1st2nd3rd4th5th

10-3 10-2 10-1 100 1010

100

200

300

400

500

Current (mA)

(c)10 k

1st2nd3rd4th5th

10-4 10-3 10-2 10-1 1000

100

200

300

400

500

1st2nd3rd4th5th

(a)1 M

Volt

age

(V)

10-2 10-1 1000

100

200

300

400(b)200 k

1st2nd3rd4th5th

10-1 100 101 1020

100

200

300

400

Current (mA)

(c)10 k

1st2nd3rd4th5th

10-3 10-2 10-1 1000

100

200

300

400(a)1 M

Volt

age

(V)

1st2nd3rd4th5th

17

3.5

3.14 5

10-3 mA 102 mA

5 Pa 20 Pa 10-3 mA 10-1 mA

10-1 mA 50 Pa 150

Pa 10-2 mA 100 mA100 mA

V p d pd

3.15 pd > (pd)min p

V pd < (pd)

min p

V

pd < (pd)min

3.14

510152050100150 Pa 10 k15 k100 k200 k1 M

10-4 10-3 10-2 10-1 100 101 1020

100

200

300

400

500

600

700

800

900

1000

Current (mA)

Volt

age

(V)

50 Pa 10 k50 Pa 200 k50 Pa 1 M

20 Pa 10 k 20 Pa 200 k20 Pa 1 M

100 Pa 10 k100 Pa 200 k100 Pa 1 M

150 Pa 10 k150 Pa 200 k150 Pa 1 M

15 Pa 15 k

10 Pa 15 k10 Pa 100 k

5 Pa 100 k5 Pa 1 M

18

3.15

3.6

3.16 Ar 20 Pa 100

4 1

3.17 20 Pa

25

10 mA-500 V 400-780 V

3.16 100

pd

V

pdmin

Vmin

10-4 10-3 10-2 10-1 100 1010

200

400

600

800

10001st2nd3rd4th

20 Pa 100

Current (mA)

Vo

ltag

e (V

)

19

3.17

3.7

3.7.1

1 1

2

nm2

[15]

2 [16] 1

2

2

100

3.7.2

P V N

k Tg Ts

=

n

=

=

P Ts

Tg V N

10-4 10-3 10-2 10-1 100 1010

200

400

600

800

1000

Current (mA)

Vo

ltag

e (V

)

40030020010025

20

n

21

4 DC DLC

DC DLC

[17-19]DLC

CO DC CVD DLC

MOSFET

DLCRF CVD

DLC

4.1 CO DLC

4.1.1

CO 2.4

0.010.2 ppm

CH4

COCO

12.574. 2 vol%CO

4.1 [20]

4.1.2 DC

4.1 DC DC

DC MOSFET

DLC 10 mA MOSFET

28.0104

-191.5

[m3/kg](1atm, 21.1) 0.861

0.967=1, 1atm, 0

3.537cm3/100cm3 H2O (1atm, 0)

CO2H2

22

4.1 DC

4.1.3

4.2 CO DC 4

Sin < 0.02 cm

4.2 CO 100 sccm (LG-11S:

ANELVA)40 Pa 300 Pa 25 300

25 kHz50 %40 Pa

RF CVD CO DLC (80

nm/min) 530

300 Pa

10

532.08 nm HORIBA JOVIN IVON HR-800

23

4.2 DC

4.2 DC

4.3(a)40 Pa (b)300 Pa DC CO

40 Pa300 Pa40 Pa

300 Pa

Si

AC 100 VDMM

5 Vp-p

CO

CO

(sccm)

(Pa)

()

(kHz)

(%)

(min)

1 25

2 300

3 25

4 100

5 200

6 300

100

40 30

300

20 50

10

24

4.3 (a)40 Pa(b)300 Pa DC CO

CVD DC

4.4 RF CVD 4.3CO

MFC 100 sccm 40 Pa RF

100 W 300 nm 4.4 RF

CVD DLC

4.4 RF CVD

4.3 RF CVD DLC

(a) 40 Pa (b) 300 Pa

CO

RF (13.56 MHz)

Si RF

G

CO

(sccm)

(Pa)

RF

(W)

(V)

(min)

100 40 100 -900 3.6

25

4.4 RF CVD DLC

4.2

4.5 DC Si CO DLC

2 40 Pa 300 87 mm

4.6(a)(b)

DC 4.6(c)

RF CVD CO DLC

1300 cm-1 1600 cm-11360

cm-1 1590 cm-1 DLC 1350 cm-1

1580 cm-1 DG

DLC

4.5 DC Si CO DLC 40 Pa

300

C2H2 CO

H(atm%)(RBS/ERDA) 27 4

O(atm%)(RBS) 0 20

(@550 nm) 2.3 2.1

(@550 nm) 0.27 0.45

(GPa) 21.5 15.1

(cm) >109 0.2

26

4.6 DC (a)40 Pa(b)300 Pa RF(c)40 Pa

4.7 DLC 2

2

1380 cm-1 D1580 cm-1

G 4.8(a)G

(cm-1)(b)G(cm-1) D I(D) G

I(G)(c)I(D)/I(G) 40 Pa 300 Pa

300 Pa GI(D)/I(G)

300 Pa 40 Pa

6 DLC

RF

CVD DLC 1 DLC

RF GI(D)/I(G)

1000 1500 2000

(c) RF 40 Pa

25

300

200

300

1000 1500 2000 1000 1500 2000

(b) Pulse 300 Pa(a) Pulse 40 Pa

25

100

Raman shift (cm-1

)

Inte

nsi

ty (

arb

. u

nit

)

27

4.7 DLC

4.8 (a)G(cm-1)(b)G(cm-1)

(c)I(D)/I(G)

1000 1500 20000

100

200

300

Raman shift (cm-1

)

Inte

nsi

ty (

arb.

unit

)

D

G

40 Pa 25

1560

1590

1620

G p

osi

tio

n (

cm-1

)

100

150

200

FW

HM

of

G p

eak

(cm

-1)

0 100 200 300

2

4

I(D

)/I(

G)

(a)

(b)

(c)

Pulse 40 PaPulse 300 PaRF 40 Pa

Electrode temperature ()

28

5

CO CVD ta-C

CVD

CVD

DC Ar

5 Pa 150 Pa

1

2

2

CVDDC CO DLC

DLC

DLC

[1] Y. Konishi, et al., Nuclear Instrument and Methods in Physics Research Section B 118(1996) 312.

[2] Y. Yasuoka et al., Japanese Journal of Applied Physics 54, 01AD04 (2015).

[3] New Diamond Vol. 28 No. 3 (2012) p7.

[4] New Diamond Vol.28 No.3 (2012) p17.

[5] Shi Xu, L. K. Cheah, B. K. Tay, Thin Solid Films, 312, 1-2, (1998), 160.

[6] , , 2011

[7] Y. Liou, R. Weimer, D. Knight, and R. Messier, Appl. Phys. Lett., 56 (1990) 437.

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(2004) L1406.

[9] J. Robertson, Diamond Relat. Mater. 2, 984(1993).

[10] K. Yamamoto et al., Diamond Relat. Mater. 10, 895(2001).

[11] J. Robertson, Diamond Relat. Mater. 3, 361(1994).

[12] Y. P. Raizer, Gas Discharge Physics (Springer Verlag. 1991).

[13] 1900

[14] 69 33 1991

[15] E.V. Alonso, R.A. Baragiola, J. Ferrn and A. Oliva-Florio, Rad. Effects 45,119 (1979).

[16] S. Hiroki et al., JAERI-M 85-123 (1985).

29

[17] T. Michler et al., Diamond Relat. Mater. 7, 459 (1998).

[18] H. Mori and H. Tachikawa, Surf. Coatings Technol. 149, 224 (2002).

[19] 50, 401 (2008).

[20] (1989)

1. Y. Yasuoka , T. Harigai, J.-S. Oh, H. Furuta, A. Hatta, T. Suzuki, and H. Saitoh, Diamond-Like

Carbon Films from CO Source Gas by RF Plasma CVD Method, Jpn. J. Appl. Phys. (accepted, 2014)

2. T. Harigai, Y. Yasuoka, N. Nitta, H. Furuta, and A. Hatta, "X-ray Reflectivity Analysis on Initial Stage

of Diamond-Like Carbon Film Deposition on Si Substrate by RF Plasma CVD and on Removal of the

Sub-Surface Layer by Oxygen Plasma Etching", Diamond Relat. Mater. 38 (2013) 36.

1. CO

RF CVD DLC2014.03.19.

2.

DLC2014.07.07.

3. CO DLC

2014.09.19.

1. Y. Yasuoka, M. Kakuta, J.-S. Oh, H. Furuta, A Hatta, Non-thermal atmospheric-pressure helium

plasma jet etched DLC film in ambient air., ISSP 2015(2015.07.09)

30