US008003497B2

(12) Ulllted States Patent (10) Patent N0.: US 8,003,497 B2

Yang et a]. (45) Date of Patent: Aug. 23, 2011

(54) DILUTED MAGNETIC SEMICONDUCTOR 6,586,095 B2 7/2003 Wang et al.

NANOWIRES EXHIBITING 7,575,631 B2 * 8/2009 Byeun et al. ................ .. 438/510
2002/0130311 A1 9/2002 Lieber et al.
MAGNETORESISTANCE 2002/0172820 A1 11/2002 Majumdar et al.
(75) Inventors: Peidong Yang, El Cerrito, CA (US); 2002/0175408 A1 11/2002 Majumdar et a1~
Heonjin Choi Seoul sangkwon 2003/0010971 A1 V2003 Zhang et
' - 2003/0039602 A1 2/2003 Sh t 1.
Lee, DaeJeon (KR); Rongrul He, arma e 3
Albany, CA (U S); Yanfeng Zhang, El OTHER PUBLICATIONS
Cerrito, CA (U S); Tevye Kuykendal, _
Berkeley CA (Us) Peter Paulauskie Stach, E.A.; PauZauskie, P.J .; Kuykendall, T.; Goldberger, J .; He, R.;
B erkel ey CA (Us), Yang, P. Watching GaN nanowires grow, Nano Letters, vol. 3, No.
_ 6, pp. 867-869 (2003).
(73) Asslgnee: The_ Regents of the University of Zhang, J .; Zhang, L. Growth of semiconductor gallium nitride
Callfornla, Oakland: CA (Us) nanowires With different catalysts, J. Vac. Sci. Technol. B. vol. 21,
(*) Notice: Subject to any disclaimer, the term of this N~ 6, PP~ 2415'2419 (2003)
patent is extended Or adjusted under 35 Kuykendall, T. et al.iMetalorganic Chemical Vapor Deposition
U'S'C~ 154(1)) by 1381 days Rout to GaN Nanowires With Triangular Cross SectionsiNano
Letters, vol. 3, No. 8, 2003, pp. 1063-1066.
(21) APP1~ NOJ 11/480,280 Zhong, Z. et al.iSynthesis of p-Type Gallium Nitride Nanowires
for Electronic and Photonic NanodevicesiNano Letters, vol. 3, No.
(22) Filed: Jun. 29, 2006 3, 2003,1313, 343.346,
Deepak, F.L. et al.iPhotoluminescence spectra and ferromagnetic
(65) Prior Publication Data properties of GaMnN nanoWiresiChemical Physical Letters 374,
Us 2009/0294908 A1 Dec. 3, 2009 2003 PP 314318
* cited by examiner
Related US. Application Data
(63) Continuation of application No. P1imary Examiner * Jack Chen
PCT/US2005/001415, ?led on Jan. 14, 2005. (74) Attorney, Agent, or Firm * John P. OBanion

(60) llroiggonal application No. 60/536,569, ?led on Jan. (57) ABSTRACT

i A method for is disclosed for fabricating diluted magnetic
(51) Int. Cl. semiconductor (DMS) nanoWires by providing a catalyst
H01L 21/20 (2006.01) coated substrate and subjecting at least a portion of the sub
(52) US. Cl. .......... .. 438/478; 438/3; 438/931; 977/762; strate to a semiconductor, and dopant via chloride-based
257/E43 .001 vapor transport to synthesize the nanoWires. Using this novel
(58) Field of Classi?cation Search ............ .. 438/3, 478, chloride-based chemical vapor transport process, single crys
438/507, 509, 931; 977/762; 257/E43_001 talline diluted magnetic semiconductor nanoWires Gal_,C
See application ?le for complete Search history, MnxN (X:0.07) Were synthesized. The nanoWires, Which
have diameters of ~10 nm to 100 nm and lengths of up to tens
(56) References Cited of micrometers, shoW ferromagnetism With Curie tempera
ture above room temperature, and magnetoresistance up to
US. PATENT DOCUMENTS 250 Kelvin.
6,130,143 A 10/2000 Westwater et al.
6,176,925 B1 1/2001 Solomon et al. 29 Claims, 22 Drawing Sheets

20
\\ 24 Semiconductor / 26
/ J Source #1
G Semiconductor /28
Source #1
32 i
29
HCL

22/ % Dopant
Source \ 3O
US. Patent Aug. 23, 2011 Sheet 1 0122 US 8,003,497 B2

20
\ 24 Semiconductor / 26
f J Source #1
G Semiconductor / 28
Source #1

32 29
HCL /

22
J X Dopant
Source \ 30

FIG. 1A

21
\ / 24
Elemental 27
Semiconductor /

G
J Source :
29
HCL /
32

X Dopant Source \ 3Q
22 J
FIG. 1B
US. Patent Aug. 23, 2011 Sheet 2 0f 22 US 8,003,497 B2

FIG. 2B
US. Patent Aug. 23, 2011 Sheet 3 0f 22 US 8,003,497 B2

3000 I | I
Ga Ga
2500 _ w E _

, i
2000 - , i -

z; : E
21500 - E E -
3 5
E K a
1000 - F 5 -
,
Cu 1
G
500 N; E a _

0 ///
2 M U
/ I
0 5 10 15 20
Photo Energy (KeV)
FIG. 2C

. L? _

- 5. 0Mn02 -_
' <>Mn203

L oMnO j
j vNanowire '

a 0
c .
5 .
O -.
o n

llllJlllllllllAl'll

610 620 630 640 650 660 670 680

Energy Loss (eV)
FIG. 2D
US. Patent Aug. 23, 2011 Sheet 4 0f 22 US 8,003,497 B2

7 o I

'r GaN:Mn NWs (2.91 eV)

GaN Nws(3.32 eV)
o '00 I

(NfEamnrios.wumen) o '0) 1

.O -I>~N
.0 I

| "f.III-IJIIIIIIIFIIIIIIJIIIIIIQ'CII
300 400 500 600 700
Wavelength (nm)
FIG. 3
US. Patent Aug. 23, 2011 Sheet 5 0f 22 US 8,003,497 B2

/50

FIG. 4B
US. Patent Aug. 23, 2011 Sheet 6 0f 22 US 8,003,497 B2

(%)MR
US. Patent Aug. 23, 2011 Sheet 7 0f 22 US 8,003,497 B2

0.72

V = 0.63 mV
0.70

A T = 4.2K

i
M

0.68 -

HO V = 2.0 mV ;/- 82
0.66 I I T
-400 -2OO O 200 400
B (mT)
FIG. 5B
US. Patent Aug. 23, 2011 Sheet 8 0f 22 US 8,003,497 B2

(Maegnmtuiz/o)
-0.6 -'

-1500 -1000 -500 0 500 1000 1500

H (Gauss)
FIG. 6A

(Maegnmtuiz/o) {b
o
o-\

F5 m
-200 -100 0 100 200
H (Gauss)
FIG. 68
US. Patent Aug. 23, 2011 Sheet 9 0f 22 US 8,003,497 B2

c3ozmu8w3
50 100 150 200 250 300
Temperature (K)
FIG. 6C
US. Patent Aug. 23, 2011 Sheet 10 0f 22 US 8,003,497 B2

1.6
' 0

1.2 - Q.
_ 0 5K .0
0.8

(Maegnmtuiz/o) 0.4

0.0

-0.4
-

-O.8 -

-1.2 -

-1.6 ' ' ' '

-6000 -4000 -2000 0 2000 4000 6000

H (Gauss)
FIG. 7A

0.10
A 0.08
2
E 0.06
a 0.04
c 0.02
-N 0.00
.5 -0.02
2 -0.04
g -0.06.
E -0.08
-0.10 ' '
-200 -100 0 100 200
H (Gauss)
FIG. 7B
US. Patent Aug. 23, 2011 Sheet 11 0122 US 8,003,497 B2

1.6

(Maegnmtuiz/o) 0.6

0.4 -

. | . l . | . | |

0 50 100 150 200 250 300

Temperature (K)
FIG. 7C
US. Patent Aug. 23, 2011 Sheet 13 0f 22 US 8,003,497 B2

100\\
112
102

114
104
112
106

FIG. 9A
US. Patent Aug. 23, 2011 Sheet 14 0f 22 US 8,003,497 B2

FIG. 10A

0.003
Current/ 100
I 4H-SIC Wafer
Q Individual GaN:Mn NW
0.002 - v 4H-SlC/'GaN:Mn NWs

9:E250 0 0. O 1 _
Current * 10

0.000

0001 -10 -8 -6 -4 -2 0
Bios Voltage (V)
FIG 10B
US. Patent Aug. 23, 2011 Sheet 15 0f 22 US 8,003,497 B2

2.35 eV

2.9 eV
120

.23 m2:5
_
_

300
3. .] 400 500
wa
360 700 800 900

._v.F MG m1Mm
m
n
I
US. Patent Aug. 23, 2011 Sheet 16 0122 US 8,003,497 B2

FIG. 11A

w
FIG. 11B
US. Patent Aug. 23, 2011 Sheet 17 0122 US 8,003,497 B2

Intesiy
0 5
Energy (KeV)
FIG. 11D
10
l
15
US. Patent Aug. 23, 2011 Sheet 18 0f 22 US 8,003,497 B2

- O -

0.0006 } 699 O {
I

0 o e . o l

00
O O OC) O bN

(Magentmizu)on -0.0002 :-
OI
{
00.0000" _:
0 o _

. O 6 0 _
-0.0006 _ O o _
_ o O :
'- l l I I l I I I I ' ' | I ' ' l ' ' ' I l l I l I I | l 1 l |

-8000 -6000 -4000 -2000 0 2000 4000 6000 8000

Field (Gauss)
FIG. 12A

0.000s_-.-..,........,.........|...-_
0.0007_
0.0006:

(Magentmizu)on 0.0005 1
0.0004

0.0003

I
l

0.0002 , H=0_02 T

0 0001 MWQMMQQMOMQM
0:1...1..,-l.--|l....l...1l.--.
0 50 100 150 200 250 300
Temperature (K)
FIG. 12B
US. Patent Aug. 23, 2011 Sheet 19 0122 US 8,003,497 B2

FIG. 13