Supporting Information

Highly Luminescent One-Dimensional Organic–Inorganic Hybrid

Double-Perovskite-Inspired Materials for Single-Component Warm
White-Light-Emitting Diodes
T. Bai, X. Wang, Z. Wang, S. Ji, X. Meng, Q. Wang, R. Zhang, P. Han, K.-l. Han, J. Chen,
F. Liu*, B. Yang*
SUPPORTING INFORMATION
Table of Contents
Experimental Materials, Synthesis, Instruments, and Characterizations
Figure S1 The octahedral connection mode, main bond lengths and bond angle of (DFPD)2KInBr6 single crystals.
(a) The survey XPS spectra and C1s XPS spectra of (a-b) DFPD-Br solid precursor and (c-d) the
Figure S2
prepared (DFPD)2KInBr6 single crystals
(a) XRD pattern (the simulated (DFPD)2KInBr6 XRD pattern was used for comparison) and (b) SEM
Figure S3
image of the microcrystals formed during the formation of (DFPD)2KInBr6 single crystals
TGA/DSC curves of the (DFPD)2KInBr6, (DFPD)2KInBr6:0.3%Sb, (DFPD)2RbInBr6,

Figure S4 (DFPD)4AgInBr8·H2O, (DFPD)2CsInBr6, and (DFPD)4InBr7 single crystals. Before 100 ℃ in the DSC

curve, the instrument is running off the baseline, and there is no phase transition
(a) Part of the single crystal structure of 1D (DFPD)2KInCl6. (b) The measured and simulated powder
Figure S5
XRD patterns for (DFPD)2KInCl6
The measured and simulated powder XRD patterns for (a) (DFPD)4AgInBr8·H2O, (b) (DFPD)2RbInBr6,
Figure S6
(c) (DFPD)4InBr7, and (d) (DFPD)2CsInBr6
PL excitation (PLE) spectra of (DFPD)4AgInBr8·H2O, (DFPD)2RbInBr6, and (DFPD)2KInBr6 single
Figure S7
crystals
CIE color coordinates, CCT, and color rendering index (CRI) of (a) (DFPD)4AgInBr8·H2O, (b)
Figure S8
(DFPD)2RbInBr6, and (c) (DFPD)2KInBr6 single crystals
(a) PL spectra and (b) the transient PL decay profiles of the (DFPD)2KInBr6 DPs with different In(OAC)3
Figure S9
manufacturers
Figure S10 PL excitation (PLE) and PL spectra of the 4,4-difluoropiperidinehydrobromic (DFPD-Br)
Figure S11 The SCXRD data from 150K and 300K for (DFPD2)KInBr6
VBM and CBM-associated charge density maps of (DFPD)2KInBr6. The charge of VBM of
Figure S12 (DFPD)2KInBr6 is mainly distributed on the Br atom; The charge distribution of CBM is mainly on the
octahedra formed by [InBr6]3-. So the electronic dimensional is 0D
PBE+SOC calculated band structure (up) and corresponding transition matrix elements (down) (in
Figure S13.
arbitrary units) for (DFPD)2KInBr6.
EDS mapping of the 0.3 mol% Sb-doped (DFPD)2KInBr6 DPs. (b) XRD patterns and (c) UV-vis
Figure S14 absorption spectra of the (DFPD)2KInBr6 DPs with various concentrations of Sb3+. The integrated PL
intensity as a function of inverse temperature for (d) the undoped and (e) Sb-doped (DFPD)2KInBr6 DPs
(a) XRD patterns, (b) UV-vis absorption spectra, (c) PL spectra and (d) the transient PL decay profiles of
Figure S15
the (DFPD)2RbInBr6 DPs with various concentrations of Sb3+
(a) XRD patterns, (b) UV-vis absorption spectra, (c) PL spectra and (d) the transient PL decay profiles of
Figure S16
the (DFPD)4AgInBr8·H2O DPs with various concentrations of Sb3+
Figure S17 (a) Contour plot of the fs TA spectra of Sb-doped (DFPD)2KInBr6 SCs
Figure S18 CIE color coordinates, CCT, and CRI of Sb-doped (DFPD)2KInBr6 thin films
Figure S19 Time-dependent PL spectra of the Sb-doped (DFPD)2KInBr6 DP thin films
Current density versus voltage for hole-only and electron-only device. the hole-only device structure
Figure S20 used in measurement is ITO/PEDOT:PSS/DP/PVK/Ag. The electron-only device used in measurement
is ITO/ZnO/DP/LiF/Al.
Figure S21 Cross-sectional SEM image of a typical LED device
(a) The current density-voltage-luminance (J-V-L) characteristics and (b) EQE for the device structure
Figure S22 used in EL measurement is ITO/PEDOT:PSS/PVK/(DFPD)2KInBr6:Sb/TPBi/LiF/Al (PVK) and
ITO/PEDOT:PSS/PVK/TCTA/(DFPD)2KInBr6:Sb/TPBi/LiF/Al (PVK+TCTA), respectively

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SUPPORTING INFORMATION
Figure S23 (a) UPS spectrum and (b) Tauc plot of the 0.3 mol% Sb-doped (DFPD)2KInBr6 DPs
Figure S24 CIE color coordinates and CRI of the warm white LEDs
EL spectra for the device structure used in EL measurement is (a) ITO/PEDOT:PSS/PVK/TPBi/LiF/Al
Figure S25 (PVK) and (b) ITO/PEDOT:PSS/PVK/TCTA/TPBi/LiF/Al (PVK+TCTA); (c) CIE color coordinates of the
EL spectra for PVK and PVK+TCTA; (d) EQE for PVK+TCTA
Figure S26 Time-dependent luminance of the LEDs operating at 8 V
Table S1 Comparison of luminescent properties of Sb-doped In-based double perovskite
Table S2 Crystal Data and Structure Refinement for (DFPD)2KInBr6 Single Crystal
Table S3 Crystal Data and Structure Refinement for (DFPD)2KInCl6 Single Crystal
Table S4 Crystal Data and Structure Refinement for (DFPD)4AgInBr8·H2O Single Crystal
Table S5 Crystal Data and Structure Refinement for (DFPD)4InBr7 Single Crystal
Table S6 Crystal Data and Structure Refinement for (DFPD)2RbInBr6 Single Crystal
Table S7 Crystal Data and Structure Refinement for (DFPD)2CsInBr6 Single Crystal
The fitted time-resolved PL decay curves lifetimes for (DFPD)2KInBr6, (DFPD)2RbInBr6,
Table S8
(DFPD)4AgInBr8·H2O
Table S9 The data of ICP-OES and the molar ratios of (DFPD)2KIn1-xSbxBr6 (0 ≤ x ≤ 0.1)
Table S10 The data of ICP-OES and the molar ratios of (DFPD)2RbIn1-xSbxBr6 (0 ≤ x ≤ 0.01)

Table S11 The data of ICP-OES and the molar ratios of (DFPD)4AgIn1-xSbxBr8 H2O(0 ≤ x ≤ 0.01)

Table S12 Summary of EL performance of some recently developed single-component white metal halide LEDs

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SUPPORTING INFORMATION
1. Materials and Synthesis
1.1 Materials
4,4-difluoropiperidine (DFPD, 97%, Bidepharm), 4,4-difluoropiperidinehydrochloride (DFPD-Cl, 97%, Bidepharm), indium
acetate (In(OAc)3, 99.99%, Aladdin), In(OAc)3 (99.99%, Sigma-Aldrich), In(OAc)3 (99.99%, Alfa Aesar), antimony acetate
(Sb(OAc)3, 99.95%, Aladdin), potassium carbonate (K2CO3, 99.95%, Aladdin), rubidium acetate (Rb(OAc), 99.95%, Aladdin),
potassium bromide (KBr, 99%, Aladdin), antimony bromide (SbBr3, 99%, Aladdin), hydrobromic acid (HBr, 40% in water,
Aladdin), triphenylphosphine oxide (98%, Innochem), poly(9-vinylcarbazole) (PVK, Sigma-Aldrich), poly(3,4-
ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS, J&K Chemicals), 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene
(TmPyPB, 99%, Xi’an Polymer Light Technology Corp), 2,2′,2″(1,3,5-benzenetriyl)tris-(1-phenyl-1H-benzimidazole) (TPBi,
99%, Xi’an Polymer Light Technology Corp), tris(4-carbazoyl-9-ylphenyl)amine (TCTA, 98%, Acme), lithium fluoride (LiF, 99%,
Sigma-Aldrich). All chemicals were used as received without further purification.

1.2 Synthesis of 4,4-difluoropiperidinehydrobromic (DFPD-Br)

1 ml of DFPD solution (dissolved in ethanol, 33 wt%) and 1~2 ml of HBr were stirred in an ice bath for 2 h to prepare DFPD-Br.
The crude DFPD-Br powder can be obtained by the evaporation of solvent at 80 °C, then purified with diethyl ether.

1.3 Synthesis of (DFPD)2KInBr6 SCs

DFPD-Br (1.6 mmol, 323 mg), K2CO3 (0.2 mmol, 28 mg), and In(OAc)3 (0.4 mmol, 117 mg) were dissolved in 1~2 ml of HBr.
The solution was heated and stirred at 363~383 K until it was completely dissolved. The crystals precipitate out after standing
overnight. Large-sized SCs can be obtained by increasing the raw material and reducing the cooling rate (about 3-5 K/day).
For Sb-doped (DFPD)2KInBr6 SCs, part of the In(OAc)3 was replaced by Sb(OAc)3, while keeping the total amount of trivalent
cations unchanged (0.4 mmol).

1.4 Synthesis of (DFPD)2KInCl6 SCs

4,4-difluoropiperidinehydrochloride (1.6 mmol, 256 mg), K2CO3 (0.2 mmol, 28 mg), and In(OAc)3 (0.4 mmol, 117 mg) were
dissolved in 0.8~1.2 ml HCl solution (30% in H2O). The solution was heated and stirred at 363~383 K until it was completely
dissolved. The crystals precipitate out after standing overnight.

1.5 Synthesis of (DFPD)4AgInBr8·H2O SCs

DFPD-Br (1.6 mmol, 323 mg), Ag2CO3 (0.2 mmol, 55 mg), and In(OAc)3 (0.4 mmol, 117 mg) were dissolved in 3 ml of HBr
solution. The solution was heated and stirred at 383~403 K until it was completely dissolved. The crystals precipitate out after
standing overnight.

1.6 Synthesis of (DFPD)4InBr7 SCs

DFPD-Br (1.6 mmol, 323 mg) and In(OAc)3 (0.4 mmol, 117 mg) were dissolved in 0.5~0.7 ml of HBr solution. The solution was
heated and stirred at 363~383 K until it was completely dissolved. The crystals precipitate out after standing overnight.

1.7 Synthesis of (DFPD)2RbInBr6 SCs

DFPD-Br (1.6 mmol, 323 mg), Rb(OAc) (0.4 mmol, 58 mg), and In(OAc)3 (0.4 mmol, 117 mg) were dissolved in 2~3 ml of HBr
solution. The solution was heated and stirred at 363~383 K until it was completely dissolved. The crystals precipitate out after
standing overnight.

1.8 Synthesis of (DFPD)2CsInBr6 SCs

DFPD-Br (1.6 mmol, 323 mg), Cs2CO3 (0.2 mmol, 65 mg), and In2O3 (0.2 mmol, 56 mg) were dissolved in 2~3 ml of HBr
solution. The solution was heated and stirred at 393~413 K until it was completely dissolved. The crystals precipitate out after
standing overnight.

1.9 (DFPD)2KInBr6 thin film deposition

Thin films of (DFPD)2KInBr6 were prepared using a methanol solution (2 mL) which contains 12 mg of (DFPD)2KInBr6. The

solution was spin-coated on an ITO glass (about 60 ℃) at 3000 rpm for 30 s (acceleration of 3000 rpm/s), then it was heated

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SUPPORTING INFORMATION
in open air at 110~130 °C for 10 minutes.

2. LED device fabrication

The ITO-coated glass substrates were rinsed with deionized water followed by sonication in deionized water, acetone, and
isopropanol, respectively, each for 15 min. The substrates were then dried at 125 ± 5 °C for 10 min and treated with UV ozone
for 10 min before use. Thereafter, the aqueous solution of PEDOT:PSS (Clevios Al 4083) filtered through a 0.45 μm PTFE
filter was spin-coated on the precleaned ITO glass at a speed of 4000 rpm for 40 s and then annealed at 125 ± 5 °C for 15
min in the ambient conditions. 1 ml of chlorobenzene solution which contains 8 mg of PVK was spin-coated on PEDOT:PSS
layer at 3000 rpm for 30 s, followed by annealing at 150 °C for 15 min in a glove box. TCTA layer was prepared by spin-
coating the prepared solution (6 mg/mL in dichloromethane) on PVK layer (3000 rpm/s, 30 s), followed by annealing at 150 °C
for 15 min in a glove box. Subsequently, thin films of Sb-doped SCs were deposited by using (DFPD)2KInBr6:Sb methanol
solution (6 mg/mL), which was dissolved with triphenylphosphine oxide (1.2 mg/mL), at 3000 rpm for 30 s, heated in open air
at 110~130 °C for 10 minutes. Then, a 45-nm-thick TPBi layer (or 45-nm-thick TmPyPB) was deposited using a vacuum
thermal evaporator. Finally, the cathode was fabricated by thermal evaporation of a LiF layer (1.0 nm), followed by an Al layer
(110 nm). Each substrate is patterned to realize three devices, each with an active area of 0.36 cm2. All the devices were
stored and characterized under the ambient atmosphere without encapsulation.

2. Measurement and characterization

2.1 Powder X-ray Diffraction (PXRD).
The phase identification was carried out using a powder X-ray diffraction in the 2Theta degree range of 5-70° with a 5° step
size (Rigaku D/max2500PC, Japan).

2.2 Single-crystal X-ray diffraction (SCXRD)

The SCXRD measurements were conducted on a SMART APEX II X-ray single-crystal diffractometer (Bruker AXS, analytical
equipment of Krasnoyarsk Center of collective use of SB RAS) equipped with a CCD detector, a graphite monochromator, and
a Mo Kα radiation source (λ = 1.5406 Å) at 150 K and 300K.

2.3 Inductively coupled plasma optical emission spectroscopy (ICP-OES) measurement.

The ICP-OES measurements were conducted using Agilent 5110 ICP-OES spectrometer.

2.4 Scanning Electron Microscope (SEM).

Field-emission scanning electron microscopy (FESEM) was carried out on a JSM-7610F instrument (Japan). EDS spectrum
was performed with an energy dispersive spectrometer equipped on the SEM equipment.

2.5 Thermogravimetric analysis (TGA).

Thermogravimetric/Synchronous Differential Thermal Analyzer TGA/DSC curve were measured with the heating rate of 10 °C
min−1 under Ar atmosphere.

2.6 Spectroscopy
UV-vis absorption spectra were recorded with a spectrophotometer (SHIMADZU UV-2600i, Japan). Photoluminescence (PL)
emission spectra and PL excitation spectra were recorded on a FLS1000 Edinburgh Instruments spectrofluorometer. PL
decay curves with short lifetime (< 5μs) were tested using a time-correlated single photon counting (TCSPC) mode. The
absolute photoluminescence (PL) quantum yield of the crystal, power and film were measured by using an integrating sphere
on an Absolute PL Quantum Yield Spectrometer (C9920-02G, Japan). The valence band potential of the material was
determined by ultraviolet photoelectron spectroscopy (UPS) (EscaLab 250Xi, Thermo, USA).

2.7 Ultrafast Transient Absorption (TA) Spectroscopy

TA Spectroscopy experiments were operated by using a home-made femtosecond pump-probe system (800 nm, 50 fs and
1KHz repetition rate) based on a regenerative amplified Ti: sapphire laser source (Hurricane, Spectra-Physics). The laser
wavelength was changed by using an optical parametric amplifier. For the probe light, we used the supercontinuum white light
generated from a thin CaF2 plate. Excitation power and spot size measurements were used to determine the excitation

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SUPPORTING INFORMATION
fluence (pump wavelength: 365 nm, pump intensity: 40µw). Transparent crystal is placed on the quartz substrate in TA
experiment.

2.8 X-ray photoelectron spectrometer (XPS)

The inner electrons or valence electrons of the atoms or molecules of the samples were determined by ThermoFischer
ESCALAB 250XI X-ray photoelectron spectrometer (XPS). The excitation source adopted Al k rays (hv = 1486.6 eV) and the
adventitious C1s peak at 284.80 eV were used as energy standard for charging correction.

2.9 LED device measurement

The EL spectra, J-V-L characteristics, and EQE were collected by using a Keithley 2400 source, a fiber integration sphere,
and a PMA-12 spectrometer for light output measurements (External quantum efficiency measurement system C9920-12,
Japan). The EQE detection limit of the instrument is in the order of 10-5%.

3.0 Theoretical calculation

First-principles calculations were performed by Vienna ab initio simulation package (VASP).[1-2] The generalized gradient
approximation (GGA) of Perdew-Burke-Ernzerh (PBE) is used to describe the exchange-correlation functional. The cut-off
energy for the plane wave basis is set to 400 eV and a 4×4×4 Monkhorst-pack mesh is employed. Relativistic SOC was
included in the band structure and optical calculations. All the structures were fully relaxed (atomic position) up to 10-5 eV/Å
force minimization and max force of 0.01 eV/Å.

3.1 Dielectric Constant Measurement

Dielectric constant tests were performed on A ZY6173 dielectric constant meter/precision LCR digital bridge TH2826 analyzer.
The sample was pressed into sheets and covered with conductive silver paste.

3.2 Carrier mobility

The carrier mobility was extracted via space-charge-limited current (SCLC) analysis. The single electron/hole devices for
current-voltage (I-V) measurement were (ITO/ZnO/(DFPD)2KInBr6:Sb/LiF/Al and ITO/PEDOT:PSS/(DFPD)2KInBr6:Sb
/PVK/Ag), respectively. As shown in the Figure S20, under low voltage (n<1), the device displays linear current response.
With the increase of voltage, the current density increases non-linearly (n>2), and the device is in the trap-filled limit (TFL)
state. In the high voltage region (n=2), the current is proportional to the square of the voltage, in accordance with Mott-Gurney
law.[3] We can use the following equation to extract the carrier mobility.

/
J = 9ɛ0ɛµV2 8L3

where J is the current density, ɛ0 = is the dielectric constant of vacuum, ɛ is the relative dielectric constant of active material, µ
is the carrier mobility, L is the thickness of active material.

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SUPPORTING INFORMATION
Table S1. Comparison of luminescent properties of Sb-doped In-based double perovskite.

Crystal Spectral
Materials PL peak (nm) PLQY (%) Ref.
dimension range (nm)
Sb-Cs2NaInCl6 3D 380-550 445 ~82 [4]
Sb-Cs2KInCl6 3D 400-700 492 ~93 [4]
Sb+Bi-Cs2NaInCl6 3D 380-800 450, 580 ~77 [5]
Sb-(PEA)2CsNaInCl7 2D 400-900 676 ~48.7 [6]
Sb-(PEA)4NaInCl8 2D 450-750 555 ~29.3 [6]
Sb-(DFPD)4AgInBr8·H2O 2D 450-900 650 ~20 This work
Sb-(DFPD)2KInCl6 1D 400-800 580 ~90 This work
Sb-(DFPD)2KInBr6 1D 450-900 610 ~92 This work
Sb-(DFPD)2RbInBr6 1D 450-900 625 ~88 This work
Sb-(DFPD)2CsInBr6 0D 450-800 580 ~90 This work
Sb-(DFPD)4InBr7 0D 500-900 660 ~46 This work

Table S2. Crystal Data and Structure Refinement for (DFPD)2KInBr6 Single Crystal.
Empirical formula C10H20N2F4InKBr6 C10H20N2F4InKBr6
Formula weight 877.66 877.66
Temperature/K 150.0 300.0
Crystal system monoclinic monoclinic
Space group P21/n P21/n
a/Å 8.8303(4) 8.8464(5)
b/Å 8.1022(4) 8.1581(4)
c/Å 16.6040(10) 16.7930(7)
α/° 90 90
β/° 103.586(2) 103.813(2)
γ/° 90 90
Volume/Å 3
1154.69(10) 1176.90(10)
Z 2 1
ρcalcg/cm 3
2.524 2.477
μ/mm -1
11.614 11.395
F(000) 816.0 816.0
Crystal size/mm 3
0.04 × 0.02 × 0.02 0.06 × 0.02 × 0.02
Radiation MoKα (λ = 0.71073) MoKα (λ = 0.71073)
2Θ range for data collection/° 6.916 to 52.78 6.888 to 52.784
Index ranges -11 ≤ h ≤ 10, -10 ≤ k ≤ 10, -20 ≤ l ≤ 20 -11 ≤ h ≤ 11, -10 ≤ k ≤ 10, -20 ≤ l ≤ 20
Reflections collected 16803 17893
Independent reflections 2327 [Rint = 0.0422, Rsigma = 0.0244] 2375 [Rint = 0.0470, Rsigma = 0.0265]
Data/restraints/parameters 2327/0/112 2375/12/112
Goodness-of-fit on F 2
1.060 1.044
Final R indexes [I >= 2σ (I)] R1 = 0.0212, wR2 = 0.0534 R1 = 0.0254, wR2 = 0.0643
Final R indexes [all data] R1 = 0.0251, wR2 = 0.0547 R1 = 0.0334, wR2 = 0.0670
Largest diff. peak/hole/eÅ -3
0.42/-0.49 0.42/-0.47

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SUPPORTING INFORMATION
Table S3. Crystal Data and Structure Refinement for (DFPD)2KInCl6 Single Crystal.
Empirical formula C10H20N2F4KInCl6
Formula weight 610.90
Temperature/K 100.02(10)
Crystal system monoclinic
Space group I2/a
a/Å 13.4003(3)
b/Å 9.4272(2)
c/Å 16.2447(4)
α/° 90
β/° 94.354(2)
γ/° 90
Volume/Å 3
2046.23(8)
Z 4
ρcalcg/cm 3
1.983
μ/mm -1
2.174
F(000) 1200.0
Crystal size/mm 3
0.1 × 0.1 × 0.02
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 5 to 58.426
Index ranges -17 ≤ h ≤ 16, -12 ≤ k ≤ 12, -19 ≤ l ≤ 22
Reflections collected 12355
Independent reflections 2409 [Rint = 0.0315, Rsigma = 0.0248]
Data/restraints/parameters 2409/0/111
Goodness-of-fit on F 2
1.064
Final R indexes [I >= 2σ (I)] R1 = 0.0199, wR2 = 0.0434
Final R indexes [all data] R1 = 0.0224, wR2 = 0.0448
Largest diff. peak/hole/eÅ -3
0.38/-0.50

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SUPPORTING INFORMATION
Table S4. Crystal Data and Structure Refinement for (DFPD)4AgInBr8·H2O Single Crystal.
Empirical formula C20H39N4F8AgInBr8·H2O

Formula weight 1368.54

Temperature/K 150.0
Crystal system monoclinic
Space group P21/n
a/Å 12.4639(4)
b/Å 11.8320(4)
c/Å 26.2029(8)
α/° 90
β/° 103.7480(10)
γ/° 90
Volume/Å 3
3753.5(2)
Z 4
ρcalcg/cm 3
2.422
μ/mm -1
9.716
F(000) 2584.0
Crystal size/mm 3
0.1 × 0.1 × 0.03
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 3.796 to 52.804
Index ranges -15 ≤ h ≤ 15, -14 ≤ k ≤ 14, -32 ≤ l ≤ 32
Reflections collected 73989
Independent reflections 7693 [Rint = 0.0714, Rsigma = 0.0349]
Data/restraints/parameters 7693/0/391
Goodness-of-fit on F 2
1.264
Final R indexes [I >= 2σ (I)] R1 = 0.0524, wR2 = 0.1312
Final R indexes [all data] R1 = 0.0734, wR2 = 0.1386
Largest diff. peak/hole/eÅ -3
1.23/-2.16

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SUPPORTING INFORMATION
Table S5. Crystal Data and Structure Refinement for (DFPD)4InBr7 Single Crystal.
Empirical formula C20H40N4F8InBr7
Formula weight 1162.75
Temperature/K 150.0
Crystal system triclinic
Space group P-1
a/Å 12.6064(7)
b/Å 12.8496(8)
c/Å 12.8662(8)
α/° 107.458(2)
β/° 104.962(2)
γ/° 102.051(2)
Volume/Å 3
1825.76(19)
Z 2
ρcalcg/cm 3
2.115
μ/mm -1
8.366
F(000) 1108.0
Crystal size/mm 3
0.04 × 0.02 × 0.02
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 3.932 to 52.76
Index ranges -15 ≤ h ≤ 15, -16 ≤ k ≤ 16, -16 ≤ l ≤ 16
Reflections collected 31554
Independent reflections 7363 [Rint = 0.0563, Rsigma = 0.0468]
Data/restraints/parameters 7363/0/361
Goodness-of-fit on F 2
1.041
Final R indexes [I >= 2σ (I)] R1 = 0.0320, wR2 = 0.0835
Final R indexes [all data] R1 = 0.0436, wR2 = 0.0887
Largest diff. peak/hole/eÅ -3
0.88/-0.69

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SUPPORTING INFORMATION
Table S6. Crystal Data and Structure Refinement for (DFPD)2RbInBr6 Single Crystal.
Empirical formula C10H20N2F4RbInBr6
Formula weight 924.03
Temperature/K 150.0
Crystal system monoclinic
Space group P21/c
a/Å 8.8137(7)
b/Å 8.1210(5)
c/Å 16.7510(15)
α/° 90
β/° 103.494(3)
γ/° 90
Volume/Å 3
1165.87(16)
Z 2
ρcalcg/cm 3
2.632
μ/mm -1
13.398
F(000) 852.0
Crystal size/mm 3
0.04 × 0.02 × 0.02
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 6.912 to 52.738
Index ranges -11 ≤ h ≤ 11, -9 ≤ k ≤ 10, -20 ≤ l ≤ 20
Reflections collected 14518
Independent reflections 2350 [Rint = 0.0440, Rsigma = 0.0300]
Data/restraints/parameters 2350/0/112
Goodness-of-fit on F 2
1.044
Final R indexes [I >= 2σ (I)] R1 = 0.0233, wR2 = 0.0590
Final R indexes [all data] R1 = 0.0291, wR2 = 0.0612
Largest diff. peak/hole/eÅ -3
0.45/-0.44

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SUPPORTING INFORMATION
Table S7. Crystal Data and Structure Refinement for (DFPD)2CsInBr6 Single Crystal.
Empirical formula C10H20N2F4CsInBr6
Formula weight 971.47
Temperature/K 150.0
Crystal system triclinic
Space group P-1
a/Å 8.1295(7)
b/Å 8.8971(7)
c/Å 17.2683(16)
α/° 103.192(3)
β/° 92.181(4)
γ/° 110.990(3)
Volume/Å 3
1125.44(17)
Z 1
ρcalcg/cm 3
2.867
μ/mm -1
13.325
F(000) 888.0
Crystal size/mm 3
0.04 × 0.02 × 0.02
Radiation MoKα (λ = 0.71073)
2Θ range for data collection/° 4.888 to 52.782
Index ranges -10 ≤ h ≤ 10, -11 ≤ k ≤ 11, -21 ≤ l ≤ 21
Reflections collected 26150
Independent reflections 4593 [Rint = 0.0610, Rsigma = 0.0393]
Data/restraints/parameters 4593/0/220
Goodness-of-fit on F 2
1.154
Final R indexes [I >= 2σ (I)] R1 = 0.0477, wR2 = 0.1134
Final R indexes [all data] R1 = 0.0555, wR2 = 0.1169
Largest diff. peak/hole/eÅ -3
1.01/-1.93

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SUPPORTING INFORMATION

Figure S1. The octahedral connection mode, main bond lengths and bond angle of (DFPD)2KInBr6 single crystals.

Figure S2. (a) The survey XPS spectra and C1s XPS spectra of (a-b) DFPD-Br solid precursor and (c-d) the prepared
(DFPD)2KInBr6 single crystals.

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Figure S3. (a) XRD pattern (the simulated (DFPD)2KInBr6 XRD pattern was used for comparison) and (b) SEM image of the
microcrystals formed during the formation of (DFPD)2KInBr6 single crystals.

Figure S4. TGA/DSC curves of the (DFPD)2KInBr6, (DFPD)2KInBr6:0.3%Sb, (DFPD)4AgInBr8·H2O, (DFPD)2RbInBr6,

(DFPD)2CsInBr6, and (DFPD)4InBr7 single crystals. Before 100 ℃ in the DSC curve, the instrument was running off the

baseline, and there is no phase transition.

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Figure S5. (a) Part of the single crystal structure of 1D (DFPD)2KInCl6. (b) The measured and simulated powder XRD
patterns for (DFPD)2KInCl6.

Figure S6. The measured and simulated powder XRD patterns for (a) (DFPD)4AgInBr8·H2O, (b) (DFPD)2RbInBr6, (c)
(DFPD)4InBr7, and (d) (DFPD)2CsInBr6.

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Figure S7. PL excitation (PLE) spectra of (DFPD)4AgInBr8·H2O, (DFPD)2RbInBr6, and (DFPD)2KInBr6 single crystals. The 320
nm and 363 nm excitation peak can be assigned as the 1S0 → 3P1 transitions of Sb3+ ions[7-9].

Figure S8. CIE color coordinates, CCT, and color rendering index (CRI) of (a) (DFPD)4AgInBr8·H2O, (b) (DFPD)2RbInBr6, and
(c) (DFPD)2KInBr6 single crystals.

Table S8. The fitted time-resolved PL decay curves lifetimes for (DFPD)2KInBr6, (DFPD)2RbInBr6, (DFPD)4AgInBr8·H2O.
Peak1 Peak2
Temperature
τ1 (ns) τ2 (ns) τave (ns) τ1 (ns) τ2 (ns) τave (ns)

KIn 300K 2443 2443 1.00 (47%) 4.20 (53%) 2.68

RbIn 300K 2374 2374 1.01 (44%) 3.72 (56%) 2.53
AgIn 300K 0.91 (32%) 4.0 (68%) 3.04 0.98 (50%) 3.44 (50%) 2.21
KIn 80K 2682 2682 2.12 (64%) 5.98 (46%) 3.53

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Table S9. The data of ICP-OES and the molar ratios of (DFPD)2KIn1-xSbxBr6 (0 ≤ x ≤ 0.1).

Element
In (mg/L) Sb (mg/L) In (%) Sb (%) PLQY (%)
Sample

In(OAC)3 (99.99%) 3.6330 0.00008 99.998 0.002 -

x=0 6.5793 0.000308 99.996 0.004 ~5
x = 0.00006 5.1781 0.000345 99.994 0.006 ~14
x = 0.0002 4.0153 0.0009 99.94 0.02 ~30
x = 0.001 6.1137 0.0087 99.97 0.13 ~86
x = 0.003 5.4230 0.0200 99.67 0.35 ~92
x = 0.01 2.4000 0.0304 98.88 1.12 ~86
x = 0.02 1.7658 0.0371 98.02 1.98 ~85
x = 0.05 1.5318 0.0937 94.23 5.77 ~82
x = 0.1 1.1893 0.1089 91.36 8.64 ~80

Table S10. The data of ICP-OES and the molar ratios of (DFPD)2RbIn1-xSbxBr6 (0 ≤ x ≤ 0.01).

Element
In (mg/L) Sb (mg/L) In (%) Sb (%) PLQY (%)
Sample
x=0 3.8880 0.000097 99.998 0.002 ~2
x = 0.001 2.1781 0.003051 99.994 0.1 ~80
x = 0.005 2.0452 0.0064 99.7 0.3 ~85
x = 0.01 2.2152 0.0216 99.1 0.9 ~82

Table S11. The data of ICP-OES and the molar ratios of (DFPD)4AgIn1-xSbxBr8·H2O(0 ≤ x ≤ 0.01).

Element
In (mg/L) Sb (mg/L) In (%) Sb (%) PLQY (%)
Sample
x=0 3.2889 0.000046 99.997 0.003 ~0.1
x = 0.001 2.0781 0.00185 99.91 0.09 ~1
x = 0.005 1.6821 0.0076 99.5 0.5 ~5
x = 0.01 1.0244 0.0094 99.12 0.88 ~10

Figure S9. (a) PL spectra and (b) the transient PL decay profiles of the (DFPD)2KInBr6 DPs with different In(OAC)3
manufacturers.

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Figure S10. PL excitation (PLE) and PL spectra of the 4,4-difluoropiperidinehydrobromic (DFPD-Br). We noted DFPD-Br
exhibited emission around 575 nm, which is similar to the position of PL peak 1 of (DFPD)4AgInBr8·H2O. Furthermore, The
PLE spectra of DFPD-Br also correspond to the PLE of peak 1 in (DFPD)4AgInBr8·H2O (Figure S7). These results indicate
that the PL peak 1 located at around 575 nm in (DFPD)4AgInBr8·H2O, which can be assigned to from the organic cation.

Figure S11. The SCXRD data from 150K and 300K for (DFPD)2KInBr6.

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Figure S12. VBM and CBM-associated charge density maps of (DFPD)2KInBr6. The charge of VBM of (DFPD)2KInBr6 is
mainly distributed on the Br atoms; The charge distribution of CBM is mainly on the octahedra formed by [InBr6]3-. So the
electronic dimensional is 0D.

Figure S13. PBE+SOC calculated band structure (up) and corresponding transition matrix elements (down) (in arbitrary units)
for (DFPD)2KInBr6.

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Figure S14. (a) EDS mapping of the 0.3 mol% Sb-doped (DFPD)2KInBr6. (b) XRD patterns and (c) UV-vis absorption spectra
of the (DFPD)2KInBr6 with various concentrations of Sb3+. The integrated PL intensity as a function of inverse temperature for
(d) the undoped and (e) Sb-doped (DFPD)2KInBr6.

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Figure S15. (a) XRD patterns, (b) UV-vis absorption spectra, (c) PL spectra and (d) the transient PL decay profiles of the
(DFPD)2RbInBr6 with various concentrations of Sb3+.

Figure S16. (a) XRD patterns, (b) UV-vis absorption spectra, (c) PL spectra and (d) the transient PL decay profiles of the
(DFPD)4AgInBr8·H2O DPs with various concentrations of Sb3+.

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Supplementary Discussion 1
To confirm the incorporation of Sb in the DP-inspired materials, EDS mapping was first carried out. From Figure S14a we
see an obvious distribution of Sb element in the SCs, indicating their presence in (DFPD)2KInBr6 DPs. Further, XRD
measurements confirm that the Sb element has entered into the crystal lattice of (DFPD)2KInBr6 because the diffraction peaks
shift toward lower angles with Sb doping (Figure S14b). Note that the actual content of Sb was determined by inductively
coupled plasma-mass spectrometry (ICP-OES). To study the effect of Sb doping on optical absorption of the (DFPD)2KInBr6,
UV-vis absorption spectrum was measured. Figure S14c shows that in these Sb3+-doped crystals, the band edge absorption
in the range of 350 to 400 nm is evidently enhanced, implying that the Sb3+ dopant has led to a stronger optical absorption for
the SCs. Similar results can be found in other In-based metal halides that contain trace amounts of Sb3+, which is believed to
result from the additional excitation associated with the 1S0 → 3P1 transitions of [SbBr6]3- in the forbidden energy gaps of the
host structures.[7-9] This also partly rationalizes the enhanced PL emission because more photogenerated carriers could be
trapped, producing the emitting STEs.[10, 11]
By fitting and comparing the temperature-dependent integrated PL intensity
(Figure S14d-e), we have also examined the influence of Sb doping on exciton thermal activation energy (Ea) of the crystals,
which is conductive to materials radiative recombination processes. It is found that the pristine samples possess Ea value of
60.3 meV, while that of the Sb-doped one has Ea value of 111.0 meV. The enhanced thermal activation energy can contribute
to a higher PLQY because it helps excitons to be localized at ambient temperature for efficient bound emission.

Figure S17. Contour plot of the fs TA spectra of Sb-doped (DFPD)2KInBr6 SCs.

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Figure S18. CIE color coordinates, CCT, and CRI of Sb-doped (DFPD)2KInBr6 thin films.

Figure S19. Time-dependent PL spectra of the Sb-doped (DFPD)2KInBr6 thin films.

Figure S20. Current density versus voltage for hole-only and electron-only device. The hole-only device structure used in
measurement is ITO/PEDOT:PSS/(DFPD)2KInBr6:Sb/PVK/Ag. The electron-only device used in measurement is
ITO/ZnO/(DFPD)2KInBr6:Sb /LiF/Al.

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Figure S21. Cross-sectional SEM image of a typical LED device of structure 3.

Figure S22. (a) The current density-voltage-luminance (J-V-L) characteristics and (b) EQE for the device structure used in EL
measurement is ITO/PEDOT:PSS/PVK/(DFPD)2KInBr6:Sb/TPBi/LiF/Al (PVK) and
ITO/PEDOT:PSS/PVK/TCTA/(DFPD)2KInBr6:Sb/TPBi/LiF/Al (PVK+TCTA), respectively.

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SUPPORTING INFORMATION

Figure S23. (a) UPS spectrum and (b) Tauc plot of the 0.3 mol% Sb-doped (DFPD)2KInBr6. UPS spectrum was recorded
using unfiltered He I excitation (21.22 eV) as the light source with the samples biased at -3.0 eV. The extrapolation of the
linear portion in the spectrum represents the positions of secondary electron cut-offs and the valence edges, indicated as
upward and downward wedge marks, respectively. Spectrum shown was displayed using the binding energy for the abscissas,
scaled from the Fermi level, which was determined from the spectrum of a thick Au film. From the secondary electron cut-off
region, the valence band maximum (VBM) of the Sb-doped sample is estimated to be 21.22 - (16.47 - 1.47) = 6.22 eV. The
band gap of the Sb-doped sample is 3.04 eV (Figure S23b), which was determined from its absorption spectrum as shown in
Figure S14c. Therefore, the conduction band minimum (CBM) is estimated to be -6.22 + 3.04 = -3.18 eV.

Table S12. Summary of EL performance of some recently developed single-component white lead-free metal halide LEDs.
Spectral range/peak Max. luminance
Emitter PLQY (%) Max. EQE (%) Ref.
(nm) (cd/m2)
375-780
Cs2AgIn0.9Bi0.1Cl6 (QD) ~31.37 ~158 ~0.08 [12]
~410, ~605
400-800
Cs2Ag0.6Na0.4InCl6:Bi 86 ± 5 ~50 - [13]
~ 559
400-700
CsCu2I3 ~20.6 ~47.5 ~0.17 [14]
~ 550
400-700
CsCu2I3+mCP ~3.23 ~14 ~0.15 [15]
~ 576
450-900 This
(DFPD)2KInBr6:Sb 50 ± 5 ~300 ~0.5
~ 610 work

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Figure S24. CIE color coordinates and CRI of the warm white LEDs.

Figure S25. EL spectra for the device structure used in EL measurement is (a) ITO/PEDOT:PSS/PVK/TPBi/LiF/Al (PVK) and
(b) ITO/PEDOT:PSS/PVK/TCTA/TPBi/LiF/Al (PVK+TCTA); (c) CIE color coordinates of the EL spectra for PVK and
PVK+TCTA; (d) EQE for PVK+TCTA.

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Figure S26. Time-dependent luminance of the LEDs operating at 8 V.

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