The optoelectronic properties of quantum confined semiconductor nanocrystals depend critically on the band edge electron and hole levels and their exciton fine structures. Transient absorption (TA) spectroscopy has been widely used to probe the dynamics of photogenerated electrons, holes, and excitons in these materials through their state filling induced bleach of the band edge exciton transition. Such effects, in principle, reflect the band edge fine structures and are well understood for the conduction band electrons. However, the valence band hole state filling signals remain poorly understood due to the complexity of the valence band level structure and the presence of fast hole trapping in many materials. Herein, we report a study of the valence band hole state filling effect by comparing the TA spectra of CdSe quantum dots (QDs) with different degrees of hole trapping and by selective removal of the conduction band electrons to adsorbed methyl viologen molecules. We observe that in CdSe/CdS core/shell QDs with a high photoluminescence quantum yield of 81%, the valence band hole contributes to 22% ± 1% of the exciton bleach, while a negligible hole state filling signal is observed in CdSe core only QDs with a photoluminescence quantum yield of 17%. This hole state filling effect can be explained by a simplified valence band edge hole model that contains two sets of twofold degenerate hole levels that are responsible for the higher energy bright exciton and lower energy dark exciton states, respectively. Our result clarifies the TA spectral features of the valence band holes and provides insights into the nature of single hole states in CdSe-based QDs.
REFERENCES
1.
A. J.
Nozik
, Physica E
14
(1–2
), 115
–120
(2002
).2.
E. H.
Sargent
, Nat. Photonics
6
(3
), 133
–135
(2012
).3.
P. V.
Kamat
, K.
Tvrdy
, D. R.
Baker
, and E. J.
Radich
, Chem. Rev.
110
(11
), 6664
–6688
(2010
).4.
X.
Dai
, Z.
Zhang
, Y.
Jin
, Y.
Niu
, H.
Cao
, X.
Liang
, L.
Chen
, J.
Wang
, and X.
Peng
, Nature
515
(7525
), 96
–99
(2014
).5.
L.
Sun
, J. J.
Choi
, D.
Stachnik
, A. C.
Bartnik
, B.-R.
Hyun
, G. G.
Malliaras
, T.
Hanrath
, and F. W.
Wise
, Nat. Nanotechnol.
7
(6
), 369
–373
(2012
).6.
O. V.
Kozlov
, Y.-S.
Park
, J.
Roh
, I.
Fedin
, T.
Nakotte
, and V. I.
Klimov
, Science
365
(6454
), 672
–675
(2019
).7.
V. I.
Klimov
, A. A.
Mikhailovsky
, S.
Xu
, A.
Malko
, J. A.
Hollingsworth
, C. A.
Leatherdale
, H.-J.
Eisler
, and M. G.
Bawendi
, Science
290
(5490
), 314
–317
(2000
).8.
D. R.
Needell
, O.
Ilic
, C. R.
Bukowsky
, Z.
Nett
, L.
Xu
, J.
He
, H.
Bauser
, B. G.
Lee
, J. F.
Geisz
, R. G.
Nuzzo
, A. P.
Alivisatos
, and H. A.
Atwater
, IEEE J. Photovoltaics
8
(6
), 1560
–1567
(2018
).9.
H.
Li
, K.
Wu
, J.
Lim
, H.-J.
Song
, and V. I.
Klimov
, Nat. Energy
1
(12
), 16157
(2016
).10.
K.
Wu
, H.
Li
, and V. I.
Klimov
, Nat. Photonics
12
(2
), 105
–110
(2018
).11.
J. M.
Pietryga
, Y.-S.
Park
, J.
Lim
, A. F.
Fidler
, W. K.
Bae
, S.
Brovelli
, and V. I.
Klimov
, Chem. Rev.
116
(18
), 10513
–10622
(2016
).12.
A. L.
Efros
and M.
Rosen
, Annu. Rev. Mater. Sci.
30
(1
), 475
–521
(2000
).13.
V. I.
Klimov
, Annu. Rev. Phys. Chem.
58
, 635
–673
(2007
).14.
W. W.
Yu
, L.
Qu
, W.
Guo
, and X.
Peng
, Chem. Mater.
15
(14
), 2854
–2860
(2003
).15.
A. L.
Efros
, M.
Rosen
, M.
Kuno
, M.
Nirmal
, D. J.
Norris
, and M.
Bawendi
, Phys. Rev. B
54
(7
), 4843
–4856
(1996
).16.
P. C.
Sercel
and A. L.
Efros
, Nano Lett.
18
(7
), 4061
–4068
(2018
).17.
M.
Korkusinski
, O.
Voznyy
, and P.
Hawrylak
, Phys. Rev. B
82
(24
), 245304
(2010
).18.
L.
Wang
, Z.
Chen
, G.
Liang
, Y.
Li
, R.
Lai
, T.
Ding
, and K.
Wu
, Nat. Commun.
10
(1
), 4532
(2019
).19.
Y.
Gao
and X.
Peng
, J. Am. Chem. Soc.
137
(12
), 4230
–4235
(2015
).20.
H.
Qin
, Y.
Niu
, R.
Meng
, X.
Lin
, R.
Lai
, W.
Fang
, and X.
Peng
, J. Am. Chem. Soc.
136
(1
), 179
–187
(2014
).21.
K.
Wu
, J.
Lim
, and V. I.
Klimov
, ACS Nano
11
(8
), 8437
–8447
(2017
).22.
K.
Wu
, Y.-S.
Park
, J.
Lim
, and V. I.
Klimov
, Nat. Nanotechnol.
12
(12
), 1140
–1147
(2017
).23.
V. I.
Klimov
, A. A.
Mikhailovsky
, D. W.
McBranch
, C. A.
Leatherdale
, and M. G.
Bawendi
, Science
287
(5455
), 1011
–1013
(2000
).24.
H.
Zhu
, Y.
Yang
, K.
Wu
, and T.
Lian
, Annu. Rev. Phys. Chem.
67
, 259
–281
(2016
).25.
H.
Zhu
, N.
Song
, W.
Rodríguez-Córdoba
, and T.
Lian
, J. Am. Chem. Soc.
134
(9
), 4250
–4257
(2012
).26.
H.
Zhu
, Y.
Yang
, K.
Hyeon-Deuk
, M.
Califano
, N.
Song
, Y.
Wang
, W.
Zhang
, O. V.
Prezhdo
, and T.
Lian
, Nano Lett.
14
(3
), 1263
–1269
(2014
).27.
J.
Huang
, Z.
Huang
, S.
Jin
, and T.
Lian
, J. Phys. Chem. C
112
(49
), 19734
–19738
(2008
).28.
J.
Huang
, D.
Stockwell
, Z.
Huang
, D. L.
Mohler
, and T.
Lian
, J. Am. Chem. Soc.
130
(17
), 5632
(2008
).29.
A.
Boulesbaa
, Z.
Huang
, D.
Wu
, and T.
Lian
, J. Phys. Chem. C
114
(2
), 962
–969
(2010
).30.
J.
Huang
, Z.
Huang
, Y.
Yang
, H.
Zhu
, and T.
Lian
, J. Am. Chem. Soc.
132
(13
), 4858
–4864
(2010
).31.
V. I.
Klimov
and D. W.
McBranch
, Phys. Rev. Lett.
80
(18
), 4028
–4031
(1998
).32.
V. I.
Klimov
, D. W.
McBranch
, C. A.
Leatherdale
, and M. G.
Bawendi
, Phys. Rev. B
60
(19
), 13740
–13749
(1999
).33.
D. P.
Morgan
and D. F.
Kelley
, J. Phys. Chem. C
124
(15
), 8448
–8455
(2020
).34.
J.
Dana
, O.
Haggag
, M.
Mor
, J.
Dehnel
, E.
Liftschitz
, and S.
Ruhman
, Nanoscale
13
, 1982
(2021
).35.
A.
Boulesbaa
, A.
Issac
, D.
Stockwell
, Z.
Huang
, J.
Huang
, J.
Guo
, and T.
Lian
, J. Am. Chem. Soc.
129
(49
), 15132
(2007
).36.
H.
Zhu
, N.
Song
, and T.
Lian
, J. Am. Chem. Soc.
133
(22
), 8762
–8771
(2011
).37.
K.
Wu
, N.
Song
, Z.
Liu
, H.
Zhu
, W.
Rodríguez-Córdoba
, and T.
Lian
, J. Phys. Chem. A
117
(32
), 7561
–7570
(2013
).38.
W.
Yang
, Y.
Yang
, A. L.
Kaledin
, S.
He
, T.
Jin
, J. R.
McBride
, and T.
Lian
, Chem. Sci.
11
(22
), 5779
–5789
(2020
).39.
K.
Wu
, Z.
Liu
, H.
Zhu
, and T.
Lian
, J. Phys. Chem. A
117
(29
), 6362
–6372
(2013
).40.
K.
Wu
, H.
Zhu
, Z.
Liu
, W.
Rodríguez-Córdoba
, and T.
Lian
, J. Am. Chem. Soc.
134
(25
), 10337
–10340
(2012
).41.
H.
Zhu
and T.
Lian
, J. Am. Chem. Soc.
134
(27
), 11289
–11297
(2012
).42.
K.
Wu
, Y.
Du
, H.
Tang
, Z.
Chen
, and T.
Lian
, J. Am. Chem. Soc.
137
(32
), 10224
–10230
(2015
).43.
K.
Wu
, J.
Chen
, J. R.
McBride
, and T.
Lian
, Science
349
(6248
), 632
–635
(2015
).44.
K.
Wu
, Q.
Li
, Y.
Du
, Z.
Chen
, and T.
Lian
, Chem. Sci.
6
(2
), 1049
–1054
(2015
).45.
Q.
Li
, F.
Zhao
, C.
Qu
, Q.
Shang
, Z.
Xu
, L.
Yu
, J. R.
McBride
, and T.
Lian
, J. Am. Chem. Soc.
140
(37
), 11726
–11734
(2018
).46.
Q.
Li
, S.
He
, and T.
Lian
, Nano Lett.
20
, 6162
(2020
).47.
Y.
Yang
, W.
Rodríguez-Córdoba
, and T.
Lian
, J. Am. Chem. Soc.
133
(24
), 9246
–9249
(2011
).48.
Y.
Yang
, W.
Rodríguez-Córdoba
, and T.
Lian
, Nano Lett.
12
(8
), 4235
–4241
(2012
).49.
Y.
Yang
, W.
Rodríguez-Córdoba
, X.
Xiang
, and T.
Lian
, Nano Lett.
12
(1
), 303
–309
(2012
).50.
I.
Kang
and F. W.
Wise
, J. Opt. Soc. Am. B
14
(7
), 1632
(1997
).51.
F. W.
Wise
, Acc. Chem. Res.
33
(11
), 773
–780
(2000
).52.
Q.
Shang
, A. L.
Kaledin
, Q.
Li
, and T.
Lian
, J. Chem. Phys.
151
(7
), 074705
(2019
).53.
K.
Wu
, G.
Liang
, Q.
Shang
, Y.
Ren
, D.
Kong
, and T.
Lian
, J. Am. Chem. Soc.
137
(40
), 12792
–12795
(2015
).54.
X.
Luo
, G.
Liang
, Y.
Han
, Y.
Li
, T.
Ding
, S.
He
, X.
Liu
, and K.
Wu
, J. Am. Chem. Soc.
142
(25
), 11270
–11278
(2020
).55.
T.
Labrador
and G.
Dukovic
, J. Phys. Chem. C
124
(15
), 8439
–8447
(2020
).56.
K. E.
Knowles
, E. A.
McArthur
, and E. A.
Weiss
, ACS Nano
5
(3
), 2026
–2035
(2011
).57.
V. I.
Klimov
, C. J.
Schwarz
, D. W.
McBranch
, C. A.
Leatherdale
, and M. G.
Bawendi
, Phys. Rev. B
60
(4
), R2177
–R2180
(1999
).58.
G.
Grimaldi
, J.
Geuchies
, W.
van der Stam
, I.
Du Fosse
, B.
Brynjarsson
, N.
Kirkwood
, S.
Kinge
, L. D. A.
Siebbeles
, and A. J.
Houtepen
, Nano Lett.
19
, 3002
(2019
).59.
D. J.
Norris
, A. L.
Efros
, M.
Rosen
, and M. G.
Bawendi
, Phys. Rev. B: Condens. Matter
53
(24
), 16347
–16354
(1996
).60.
M.
Nirmal
, D. J.
Norris
, M.
Kuno
, M. G.
Bawendi
, A. L.
Efros
, and M.
Rosen
, Phys. Rev. Lett.
75
(20
), 3728
–3731
(1995
).61.
M.
Kuno
, J. K.
Lee
, B. O.
Dabbousi
, F. V.
Mikulec
, and M. G.
Bawendi
, J. Chem. Phys.
106
(23
), 9869
–9882
(1997
).62.
C.
de Mello Donegá
, M.
Bode
, and A.
Meijerink
, Phys. Rev. B
74
(8
), 085320
(2006
).63.
E.
Cassette
, S.
Pedetti
, B.
Mahler
, S.
Ithurria
, B.
Dubertret
, and G. D.
Scholes
, Phys. Chem. Chem. Phys.
19
(12
), 8373
–8379
(2017
).64.
D. A.
Hanifi
, N. D.
Bronstein
, B. A.
Koscher
, Z.
Nett
, J. K.
Swabeck
, K.
Takano
, A. M.
Schwartzberg
, L.
Maserati
, K.
Vandewal
, Y.
van de Burgt
, A.
Salleo
, and A. P.
Alivisatos
, Science
363
(6432
), 1199
–1202
(2019
).65.
L. E.
Brus
, J. Chem. Phys.
79
(11
), 5566
–5571
(1983
).66.
L. E.
Brus
, J. Chem. Phys.
80
(9
), 4403
–4409
(1984
).67.
Q.
Li
, K.
Wu
, J.
Chen
, Z.
Chen
, J. R.
McBride
, and T.
Lian
, ACS Nano
10
(3
), 3843
–3851
(2016
).68.
H.
Zhu
, N.
Song
, and T.
Lian
, J. Am. Chem. Soc.
132
(42
), 15038
–15045
(2010
).69.
P.
Zeng
, N.
Kirkwood
, P.
Mulvaney
, K.
Boldt
, and T. A.
Smith
, Nanoscale
8
(19
), 10380
–10387
(2016
).70.
H.
Zhu
, N.
Song
, H.
Lv
, C. L.
Hill
, and T.
Lian
, J. Am. Chem. Soc.
134
(28
), 11701
–11708
(2012
).71.
D. J.
Norris
, A.
Sacra
, C. B.
Murray
, and M. G.
Bawendi
, Phys. Rev. Lett.
72
(16
), 2612
–2615
(1994
).72.
Y.
Wang
, A.
Suna
, J.
McHugh
, E. F.
Hilinski
, P. A.
Lucas
, and R. D.
Johnson
, J. Chem. Phys.
92
(11
), 6927
–6939
(1990
).73.
Y.-S.
Park
, J.
Lim
, and V. I.
Klimov
, Nat. Mater.
18
(3
), 249
–255
(2019
).74.
A. I.
Ekimov
, I. A.
Kudryavtsev
, A. L.
Efros
, T. V.
Yazeva
, F.
Hache
, M. C.
Schanne-Klein
, A. V.
Rodina
, D.
Ricard
, and C.
Flytzanis
, J. Opt. Soc. Am. B
10
(1
), 100
(1993
).75.
K.
Leung
, S.
Pokrant
, and K. B.
Whaley
, Phys. Rev. B
57
(19
), 12291
–12301
(1998
).76.
O.
Labeau
, P.
Tamarat
, and B.
Lounis
, Phys. Rev. Lett.
90
(25
), 257404
(2003
).77.
A.
Shabaev
, A. V.
Rodina
, and A. L.
Efros
, Phys. Rev. B
86
(20
), 205311
(2012
).© 2022 Author(s). Published under an exclusive license by AIP Publishing.
2022
Author(s)
You do not currently have access to this content.
