Nanoco Technologies Ltd. v. Samsung Electronics Co., Ltd. et al

Filing 1

COMPLAINT against Samsung Advanced Institute of Technology, Samsung Display Co., Ltd., Samsung Electronics America, Inc., Samsung Electronics Co., Ltd., Samsung Electronics Co., Ltd. Visual Display Division ( Filing fee $ 400 receipt number 0540-7664317.), filed by Nanoco Technologies Ltd.. (Attachments: # 1 Civil Cover Sheet, # 2 Exhibit 1, # 3 Exhibit 2, # 4 Exhibit 3, # 5 Exhibit 4, # 6 Exhibit 5, # 7 Exhibit 6, # 8 Exhibit 7, # 9 Exhibit 8, # 10 Exhibit 9, # 11 Exhibit 10, # 12 Exhibit 11, # 13 Exhibit 12, # 14 Exhibit 13, # 15 Exhibit 14)(Henry, Claire)

Exhibit 14

Supporting Information

Bright and Uniform Green Light Emitting
InP/ZnSe/ZnS Quantum Dots for Wide Color Gamut
Displays
Yongwook Kim†∥, Sujin Ham‡∥ Hyosook Jang†, Ji Hyun Min†, Heejae Chung†, Junho Lee†,
Dongho Kim‡* and Eunjoo Jang†*

†

Inorganic Material Lab, Samsung Advanced Institute of Technology, Samsung Electronics, 130
Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 16678, Republic of Korea.
‡

Department of Chemistry, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 03722,
Republic of Korea.
∥These

authors contributed equally to this work.

*E mail: [e-mail]; [e-mail]

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Table of Contents
1. Supporting Figures and Table
2. References

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1. Supporting Figures and Table
a

In(LA)3

150°C

In-P-Zn ligand
complex
Zn(OA)2 (TMS)3P

170°C

InP-Zn
magic-sized cluster
(labs = 370 nm)

240°C

InP
Growth and Focusing

b

Intensity

150°C
170°C
240°C

300

400

500
Wavelength (nm)
180

c

600

700

d =2.0 nm
σ = 12%

160
140
Counts

120
100
80
60
40

20
20 nm

0
0

1

2

3

4 5 6 7
Diameter (nm)

8

9 10 11

d
(TMS)3P injection at
150°C

Intensity

280°C

300

400

500
Wavelength (nm)

600

700

Figure S1. (a) Scheme of the InP core growth. (b) Absorption spectrum evolution during the InP
growth. (c) A STEM image (left) and the size distribution (right) of InP cores. The black line in
the size distribution is the Gaussian fit. (d) Comparison of absorption spectra of InP QDs
prepared by injecting (TMS)3P at 150°C and 280°C.

S-3

Table S1. Elemental compositions of QDs and calculated thickness of each shell as well as the
diameter of QDs.

Sample

Mole ratio (X/In)

Thickness (nm)

Diameter

ZnSe

ZnS

ZnSe/ZnS

(nm)

1.00

-

-

-

2.0

15.3

1.00

1.5

-

1.5

5.0

34.9

15.3

1.00

1.5

0.5

2.0

6.0

10.3

0.00

1.00

-

1.0

1.0

4.0

P/In

S/In

Zn/In Se/In In/In

InP

0.73

0.00

0.37

0.00

InP/ZnSe

0.57

0.00

16.7

InP/ZnSe/ZnS

0.67

14.7

InP/ZnS

0.67

8.45

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60
a

InP/ZnSe

d = 5.3 nm
σ = 15%

Counts

40

20

0

0

1

2

3

4

5

6

7

20
b

8

9 10 11

d = 7.3 nm
σ = 16%

InP/ZnSe/ZnS

Counts

15

10

5

0
0

1

2

3

4

5

6

7

8

9 10 11

120

c

d = 4.2 nm
σ = 12%

InP/ZnS
100

Counts

80

60
40
20

20 nm

0
0

1

2

3

4 5 6 7
Diameter (nm)

8

9 10 11

Figure S2. STEM images (left) and their corresponding size distributions (right) of InP/ZnSe (a),
InP/ZnSe/ZnS (b), and InP/ZnS QDs (c). Black lines indicate Gaussian fitting of the size
distribution.

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HAADF

In

P

Se

S

10 nm

Zn

Figure S3. STEM EDS mapping images of InP/ZnSe/ZnS QDs.

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a

Intensity

InP/ZnS

300

400

500

600

700

Wavelength (nm)
b

c

2 nm

20 1/nm

d

Intensity

InP/ZnS

10

20

30

40
50
2 Theta (deg)

60

70

Figure S4. (a) Absorption (dotted lines) and emission (solid lines) spectra of InP/ZnS QDs. A
HR-STEM image (b) and its FFT diffractogram (c) of InP/ZnS QD. (d) Powder XRD patterns of
InP/ZnS QDs. The vertical bars represent the diffraction patterns for bulk zinc-blende ZnS.

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PL Intensity

InP/ZnS
InP/ZnSe
InP/ZnSe/ZnS

400

450

500
550
Wavelength (nm)

600

650

Figure S5. Steady-state emission spectra for InP/ZnS, InP/ZnSe, and InP/ZnSe/ZnS. Fitting each
emission spectrum to a Gaussian function (short gray dashes) at the front line creates a tail on the
right side of the spectrum. The percentage of the tail is 14% of InP/ZnS, 29% of InP/ZnSe, and
11% of InP/ZnSe/ZnS.

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0

100
10

InP/ZnS

610
10 -1
10-1
450

PL Intensity (counts / 20 ms)

10 -2
10-2

0
0

100
100

200
200

300
300

400
400

1000

10

500
500

InP/ZnSe
635

-1
10-1

10

470
-2
10-2

0
0

100
100

200
200

300
300

0
100

10

400
400

500
500

InP/ZnSe/ZnS

10-1
10-1
610
470

10-2
10-2

0

100
100

200
200

300
300
Time (ns)

400
400

500
500

Figure S6. Time-resolved PL decay curves probed at different wavelengths with a 10 nm
spectral width for InP/ZnS (top), InP/ZnSe (middle), and InP/ZnSe/ZnS (bottom).

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InP/ZnS

PL Intensity (norm.)

InP/ZnSe

Temp. (K)
77
97
117
137
157
177
197
217
237
257
277
297

InP/ZnSe/ZnS

450

500

550
600 650
700
Wavelength (nm)

750

Figure S7. Normalized temperature-dependent PL spectra of the InP/ZnS (top), InP/ZnSe
(middle), and InP/ZnSe/ZnS (bottom) QDs

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Se 2P3/2

InP/ZnS
InP/ZnSe
InP/ZnSe/ZnS

Se–O

Se 3d

S 2P

b

Intensity

Se 2P1/2

a

172

168
164
160
Binding Energy (eV)

156

68

64

60
56
Binding Energy (eV)

52

Figure S8. S (2P) and Se (2P1/2) peaks (a) and Se (3d) peak (b) of high-resolution XPS spectra of
InP/ZnSe (dark cyan), InP/ZnSe/ZnS (green) and InP/ZnS QDs (navy).

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a 2.55
InP/ZnS
InP/ZnSe
InP/ZnSe/ZnS

Energy (eV)

2.50

2.45

2.40

2.35

2.30
50

100

b 260

150
200
Temperature (K)

250

300

250

300

InP/ZnS
InP/ZnSe
InP/ZnSe/ZnS

240

FWHM (meV)

220
200
180
160
140
120

50

100

150
200
Temperature (K)

Figure S9. Temperature-dependent PL peak energy (a) and FWHM (b) of the InP/ZnSe,
InP/ZnSe/ZnS, and InP/ZnS QDs.

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1S

Energy

Surface

Core

GS

Configuration coordinate (a.u.)

Figure S10. Schematics of core and surface emission for the QDs. In this approach, described by
Marcus-Jortner electron transfer theory1, the possibility of tunneling through the potential barrier
is explicitly allowed via a minimal model consisting of two modes: a classical low-frequency
mode representing interaction with the medium, and a quantum high-frequency mode
representing internal vibrations. The classical mode governs the high-temperature and thermally
activated population equilibria, and the quantum mode governs the low-temperature populations
via tunneling as well as spectral line shapes.

S-13

a

InP/ZnS
InP/ZnSe
InP/ZnSe/ZnS

b

InP/ZnS
InP/ZnSe
InP/ZnSe/ZnS
αoff = 1.43

αoff = 1.46

αon = 1.38

αoff = 1.42

αon = 1.25

10-1
c

101
ton (s)

P[toff] (s -1)

P[ton] (s -1)

αon = 1.33

103

10-1

core/shell

101
toff (s)

103

core/shell/shell
Charged
state

Charged
state

ΔE2
ΔE1

ΔE2

ΔE1

Neutral state

Neutral state

Figure S11. On- (a) and off-time (b) probability density plots calculated using more than 100
single QDs, and fitted using truncated power-law and power-law equations, respectively, with a
high value of adjusted r-square (0.99). (c) A schematic of the charge trapping (blue arrows) and
detrapping (pink arrows) processes.

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Relative PL Intensity (%)

540

100

536

95

532

90

528

85

524

80

PL Wavelength (nm)

105

520
0

10

20

30
Time (h)

40

50

60

Figure S11. Photostability of the InP/ZnSe/ZnS QDs. Relative PL intensity (green) and PL
wavelength (blue) changes over time.

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2. References
1. Mooney, J.; Krause, M. M.; Saari, J. I.; Kambhampati, P. Challenge to the Deep-trap
Model of the Surface in Semiconductor Nanocrystals Phys. Rev. B 2013, 87, 081201.

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