Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 1 of 17 PageID #: 307
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`Exhibit 14
`
`
`
`Exhibit 14
`
`
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`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 2 of 17 PageID #: 308
`
`
`
`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: ejjang12@samsung.com; dongho@yonsei.ac.kr
`
`
`
`S-1
`
`
`
`
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`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 3 of 17 PageID #: 309
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`Table of Contents
`
`1. Supporting Figures and Table
`
`2. References
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`
`
`
`
`
`
`S-2
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`
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`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 4 of 17 PageID #: 310
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`1. Supporting Figures and Table
`
`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
`
`a
`
`In(LA)3
`
`150°C
`
`Zn(OA)2
`
`(TMS)3P
`
`In-P-Zn ligand
`complex
`
`170°C
`
`InP-Zn
`magic-sized cluster
`(labs = 370 nm)
`
`240°C
`
`InP
`Growth and Focusing
`
`150°C
`170°C
`240°C
`
`d =2.0 nm
`σ = 12%
`
`300
`
`400
`
`500
`Wavelength (nm)
`180
`
`600
`
`700
`
`160
`
`140
`
`120
`
`100
`
`80
`
`60
`
`40
`
`20
`
`0
`
`Counts
`
`20 nm
`
`0
`
`1
`
`2
`
`3
`
`4
`5
`6
`7
`Diameter (nm)
`
`8
`
`9 10 11
`
`(TMS)3P injection at
`150°C
`280°C
`
`300
`
`400
`
`500
`Wavelength (nm)
`
`600
`
`700
`
`Intensity
`
`b
`
`Intensity
`
`d
`
`c
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`
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`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 5 of 17 PageID #: 311
`
`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
`
`P/In S/In Zn/In Se/In
`
`In/In ZnSe
`
`ZnS ZnSe/ZnS
`
`(nm)
`
`InP
`
`0.73 0.00 0.37 0.00 1.00
`
`-
`
`InP/ZnSe
`
`0.57 0.00 16.7 15.3 1.00
`
`1.5
`
`InP/ZnSe/ZnS
`
`0.67 14.7 34.9 15.3 1.00
`
`1.5
`
`InP/ZnS
`
`0.67 8.45 10.3 0.00 1.00
`
`-
`
`-
`
`-
`
`0.5
`
`1.0
`
`-
`
`1.5
`
`2.0
`
`1.0
`
`2.0
`
`5.0
`
`6.0
`
`4.0
`
`
`
`
`
`S-4
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 6 of 17 PageID #: 312
`
`
`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.
`
`
`
`S-5
`
`d = 5.3 nm
`σ = 15%
`
`0
`
`1
`
`2
`
`3
`
`4
`
`5
`
`6
`
`7
`
`8
`
`9 10 11
`
`d = 7.3 nm
`σ = 16%
`
`0
`
`1
`
`2
`
`3
`
`4
`
`5
`
`6
`
`7
`
`8
`
`9 10 11
`
`d = 4.2 nm
`σ = 12%
`
`0
`
`1
`
`2
`
`3
`
`4
`5
`6
`7
`Diameter (nm)
`
`8
`
`9 10 11
`
`60
`
`40
`
`20
`
`0
`
`20
`
`15
`
`10
`
`5
`
`0
`
`Counts
`
`Counts
`
`120
`
`100
`
`80
`
`60
`
`40
`
`20
`
`0
`
`Counts
`
`a
`
`InP/ZnSe
`
`b
`
`InP/ZnSe/ZnS
`
`c
`
`InP/ZnS
`
`20 nm
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 7 of 17 PageID #: 313
`
`Figure S3. STEM EDS mapping images of InP/ZnSe/ZnS QDs.
`
`
`
`
`
`
`
`S-6
`
`HAADF
`
`In
`
`10 nm
`
`Zn
`
`Se
`
`P
`
`S
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 8 of 17 PageID #: 314
`
`
`
`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.
`
`
`
`
`
`
`
`S-7
`
`InP/ZnS
`
`300
`
`400
`
`500
`
`600
`
`700
`
`Wavelength (nm)
`
`c
`
`
`
`a
`
`Intensity
`
`b
`
`
`
`
`
`
`
`
`
`
`
`
`
`2 nm
`
`20 1/nm
`
`InP/ZnS
`
`d
`
`Intensity
`
`10
`
`20
`
`30
`
`40
`
`50
`
`60
`
`70
`
`2 Theta (deg)
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
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`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 9 of 17 PageID #: 315
`
`
`
`
`
`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.
`
`
`
`
`
`
`
`
`
`S-8
`
`InP/ZnS
`InP/ZnSe
`InP/ZnSe/ZnS
`
`PL Intensity
`
`400
`
`450
`
`500
`550
`Wavelength (nm)
`
`600
`
`650
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 10 of 17 PageID #: 316
`
`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).
`
`
`
`
`
`
`
`
`
`
`
`S-9
`
`InP/ZnS
`
`610
`
`450
`
`0
`
`100
`
`200
`
`300
`
`400
`
`500
`
`InP/ZnSe
`
`635
`
`470
`
`0
`
`100
`
`200
`
`300
`
`400
`
`500
`
`InP/ZnSe/ZnS
`
`610
`
`470
`
`0
`
`100
`
`200
`300
`Time (ns)
`
`400
`
`500
`
`100
`
`10-1
`
`10-2
`
`100
`
`10-1
`
`10-2
`
`100
`
`10-1
`
`10-2
`
`PL Intensity (counts / 20 ms)
`
`100
`
`10-1
`
`10-2
`
`0
`
`100
`
`200
`
`300
`
`400
`
`500
`
`100
`
`10-1
`
`10-2
`
`0
`
`100
`
`200
`
`300
`
`400
`
`500
`
`100
`
`10-1
`
`10-2
`
`0
`
`100
`
`200
`
`300
`
`400
`
`500
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 11 of 17 PageID #: 317
`
`Figure S7. Normalized temperature-dependent PL spectra of the InP/ZnS (top), InP/ZnSe
`
`(middle), and InP/ZnSe/ZnS (bottom) QDs
`
`
`
`
`
`
`
`
`
`S-10
`
`InP/ZnS
`
`InP/ZnSe
`
`Temp. (K)
`77
`97
`117
`137
`157
`177
`197
`217
`237
`257
`277
`297
`
`InP/ZnSe/ZnS
`
`PL Intensity (norm.)
`
`450
`
`500
`
`550
`600
`650
`Wavelength (nm)
`
`700
`
`750
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 12 of 17 PageID #: 318
`
`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).
`
`
`
`
`
`
`
`
`
`S-11
`
`Se 3d
`
`Se–O
`
`b
`
`InP/ZnS
`
`InP/ZnSe
`
`InP/ZnSe/ZnS
`
`Se 2P3/2
`
`S 2P
`
`Se 2P1/2
`
`a
`
`Intensity
`
`172
`
`168
`
`164
`
`160
`
`156
`
`68
`
`64
`
`60
`
`56
`
`52
`
`Binding Energy (eV)
`
`Binding Energy (eV)
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 13 of 17 PageID #: 319
`
`Figure S9. Temperature-dependent PL peak energy (a) and FWHM (b) of the InP/ZnSe,
`
`InP/ZnSe/ZnS, and InP/ZnS QDs.
`
`
`
`
`
`
`
`
`
`S-12
`
`InP/ZnS
`InP/ZnSe
`InP/ZnSe/ZnS
`
`50
`
`100
`
`150
`
`200
`
`250
`
`300
`
`Temperature (K)
`
`InP/ZnS
`InP/ZnSe
`InP/ZnSe/ZnS
`
`50
`
`100
`
`150
`200
`Temperature (K)
`
`250
`
`300
`
`a
`
`2.55
`
`2.50
`
`2.45
`
`2.40
`
`2.35
`
`2.30
`
`Energy (eV)
`
`b
`
`260
`
`240
`
`220
`
`200
`
`180
`
`160
`
`140
`
`120
`
`FWHM (meV)
`
`
`
`
`
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 14 of 17 PageID #: 320
`
`
`
`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
`
`1S
`
`GS
`
`Core
`
`Surface
`
`Energy
`
`Configuration coordinate (a.u.)
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 15 of 17 PageID #: 321
`
`
`
`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.
`
`
`
`
`
`
`
`S-14
`
`a
`
`InP/ZnS
`InP/ZnSe
`InP/ZnSe/ZnS
`
`b
`
`InP/ZnS
`InP/ZnSe
`InP/ZnSe/ZnS
`
`αon = 1.33
`
`αoff = 1.43
`
`P[toff] (s-1)
`
`αoff = 1.46
`
`αoff = 1.42
`
`αon = 1.38
`
`αon = 1.25
`
`P[ton] (s-1)
`
`10-1
`
`101
`ton (s)
`
`core/shell
`
`c
`
`103
`
`10-1
`
`101
`toff (s)
`
`103
`
`core/shell/shell
`
`Charged
`state
`
`Charged
`state
`
`ΔE2
`
`ΔE1
`
`ΔE1
`
`ΔE2
`
`Neutral state
`
`Neutral state
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 16 of 17 PageID #: 322
`
`Figure S11. Photostability of the InP/ZnSe/ZnS QDs. Relative PL intensity (green) and PL
`
`wavelength (blue) changes over time.
`
`
`
`
`
`
`
`
`
`
`
`S-15
`
`PL Wavelength (nm)
`
`540
`
`536
`
`532
`
`528
`
`524
`
`520
`
`10
`
`20
`
`30
`Time (h)
`
`40
`
`50
`
`60
`
`105
`
`100
`
`95
`
`90
`
`85
`
`Relative PL Intensity (%)
`
`80
`
`0
`
`
`
`
`
`
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-15 Filed 02/14/20 Page 17 of 17 PageID #: 323
`
`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.
`
`
`
`
`
`S-16
`
`
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