Perovskite-Based Near-Infrared Photodetectors

doi:10.7536/PC230526

In recent years, organo-metal halide perovskites materials with ABX₃ crystal structure have shown promising application prospects in the field of photoelectric detection due to their optical and electrical properties such as adjustable bandgap engineering, high absorption coefficient and long carrier transmission distance. Especially, the hybrid perovskite prepared by pure Sn or Sn/Pb mixed cations have excellent near-infrared photoelectroresponse in the range of 760~1050 nm, showing many advantages such as high sensitivity, low dark current and high detection rate. To further broaden the near-infrared and infrared response wavelength range of perovskite, the researchers explored combining organic materials, crystalline silicon/germanium, Ⅲ-Ⅴ compounds, Ⅳ-Ⅵ compounds, upconversion fluorescent materials as complementary light absorption layers with perovskite to prepare heterostructures to construct wide-spectrum response near-infrared photodetectors. Based on the above research, this paper summarizes the current effective ways to broaden the spectrum range of perovskite photodetectors. At the same time, the future development prospect of perovskite material near infrared photodetector is prospected.

Contents

1 Introduction

2 Basic indicators of photodetectors

2.1 Device structure and working principle of photodetectors

2.2 Performance parameters of photodetectors

2.3 Strategy of broadening the spectrum response range of perovskites

3 Pb perovskite for near-infrared photodetectors

3.1 Polycrystalline perovskite materials

3.2 Single crystal perovskite materials

4 Narrow band gap Sn and Sn/Pb Mixed Perovskite- Based near-infrared photodetectors

4.1 Sn-based perovskite near-infrared photodetectors

4.2 Sn/Pb mixed perovskite near-infrared photodetectors

5 Perovskite/inorganic heterojunction near-infrared photodetectors

5.1 Silicon and other classic semiconductors

5.2 Graphene

5.3 Transition metal dichalcogenides

5.4 Ⅲ-Ⅴ compounds semiconductors

5.5 Ⅳ-Ⅳ compounds semiconductors

6 Perovskite/organic heterojunction near-infrared photodetectors

7 Perovskite/upconversion material near-infrared photodetectors

8 Application of near-infrared photodetectors

9 Conclusion and outlook

Key words: optical device, perovskite, near-infrared photodetectors, narrow-bandgap materials

Fig.2 Three different types of perovskite PDs schematic (a) photodiode; (b) photoconductive type; (c) phototransistor.

Fig.3 (a) Energy level matching diagram of ZnO nanorods/ MAPbI3 PDs[17];(b) Schematic diagram of MAPbI3-xClx for flexible devices[18];(c) Photocurrent and responsivity of MAPbI3 nanocrystalline PDs[19];(d) Photographs of MAPbI3 single crystals[21];(e) Response velocity curves of MAPbI3 single crystals [22];(f) MAPbI3 single crystal space charge limiting current test (SCLC)[23] Copyright 2017, American Chemical Society. Copyright 2017, Nature. Copyright 2020, Wiley-VCH. Copyright 2016, Wiley-VCH. Copyright 2018, Elsevier. Copyright 2022, Royal Society of Chemistry.

Table 1 Common Sn and Sn?Pb Perovskite NIR-PDs

Perovskite	Wavelength range (nm)	Responsivity (mA·W⁻¹)	Detection rate (Jones)	EQE (%)	LDR (dB)	Response time [t_rise/t_decay]	Ref.
MASnI₃	300~1000	470	8.8×10¹⁰			1.5 s/0.4 s	30
CsSnI₃	475~940	54 @940 nm	3.85×10⁵			83.8 ms/243 ms	31
CsSnI₃	400~900	257	1.5×10¹¹			0.35 ms/1.6 ms	32
FASnI₃	300~1000						33
FASnI₃	300~1000	1.1×10⁸	1.9×10¹²			180 s/360 s	34
FASnI₃	300~1000	2×10⁸ @850 nm	3.2×10¹²			117 s/206 s	35
PEA_0.15FA_0.85SnI₃	450~850	0.39	8.29 × 10¹¹			0.78 μs	50
MA_0.975Rb_0.025Sn_0.65Pb_0.35I₃	300~1100	400 @910 nm	>10¹²		110	40 ns/468 ns	38
MASn_xPb_1-xI₃	300~1100	200 @940 nm	>10¹¹	>20% @780-970 nm	100	0.09 μs /2.27 μs	39
FA_0.85Cs_0.15Sn_0.5Pb_0.5I₃	600~1000	530 @940 nm	6 ×10¹²	≈80% @ 760-900 nm	103	58.3 ns/0.86 μs	40
(FASnI₃)_0.6(MAPbI₃)_0.4	300~1000	400 @950 nm	1.1 × 10¹²	>65% @350-900 nm	167	6.9 μs/9.1 μs	14
Cs_0.05MA_0.45FA_0.5Pb_0.5Sn_0.5I₃	300~1050	530 @910 nm	2.01 × 10¹¹			0.035 μs	41
CsPb_0.5Sn_0.5I₃ (5% (PEA)₂Pb_0.5Sn_0.5I₄)	700~900	270 @850 nm	5.42×10¹⁴				42
MA_0.5FA_0.5Pb_0.5Sn_0.5I₃(2.5% (PEA)₂Pb_0.5Sn_0.5I₄)	700~900	≈100 @800 nm	≈1.6 × 10¹²	≈14% @800 nm		10 μs /10 μs	51
(MAPbI₃)_0.5(FASnI₃)_0.5	300~1050	410	2.91×10¹²	>60 @808 nm		10.9 ms/8.9 ms	43
MA_0.5FA_0.5Pb_0.5Sn_0.5I₃	350~1000	>200 @ 800~950 nm	>10¹²	≈10% @800 nm			44
MA_0.3FA_0.7Pb_0.5Sn_0.5I₃	470~910	600	1.5 × 10¹²	85% @850 nm			45
FA_0.5MA_0.45Cs_0.05Pb_0.5Sn_0.5I₃	300~1050	350 @950 nm	2.21 × 10¹¹	75% @800 nm	185	42.9 ns	46
Cs_0.15FA_0.85Pb_0.5Sn_0.5I₃	300~1050	520 @850 nm	5.34 × 10¹²	75% @850 nm	224	39.68 ns	47
FA_0.7MA_0.3Sn_0.5Pb_0.5I₃	450~900	510	1.8 × 10¹²	75.4% @840 nm		94 ns/97 ns	48
FA_0.85Cs_0.15Sn_0.5Pb_0.5I₃	400~900	570	8.48 × 10¹²	80 @910 nm		67.5 ns/0.72 μs	49
MASn_0.25Pb_0.75I₃	500~900	510	1.1 × 10¹³		192.6		52

Table 1 Common Sn and Sn?Pb Perovskite NIR-PDs

Perovskite	Wavelength range (nm)	Responsivity (mA·W⁻¹)	Detection rate (Jones)	EQE (%)	LDR (dB)	Response time [t_rise/t_decay]	Ref.
MASnI₃	300~1000	470	8.8×10¹⁰			1.5 s/0.4 s	30
CsSnI₃	475~940	54 @940 nm	3.85×10⁵			83.8 ms/243 ms	31
CsSnI₃	400~900	257	1.5×10¹¹			0.35 ms/1.6 ms	32
FASnI₃	300~1000						33
FASnI₃	300~1000	1.1×10⁸	1.9×10¹²			180 s/360 s	34
FASnI₃	300~1000	2×10⁸ @850 nm	3.2×10¹²			117 s/206 s	35
PEA_0.15FA_0.85SnI₃	450~850	0.39	8.29 × 10¹¹			0.78 μs	50
MA_0.975Rb_0.025Sn_0.65Pb_0.35I₃	300~1100	400 @910 nm	>10¹²		110	40 ns/468 ns	38
MASn_xPb_1-xI₃	300~1100	200 @940 nm	>10¹¹	>20% @780-970 nm	100	0.09 μs /2.27 μs	39
FA_0.85Cs_0.15Sn_0.5Pb_0.5I₃	600~1000	530 @940 nm	6 ×10¹²	≈80% @ 760-900 nm	103	58.3 ns/0.86 μs	40
(FASnI₃)_0.6(MAPbI₃)_0.4	300~1000	400 @950 nm	1.1 × 10¹²	>65% @350-900 nm	167	6.9 μs/9.1 μs	14
Cs_0.05MA_0.45FA_0.5Pb_0.5Sn_0.5I₃	300~1050	530 @910 nm	2.01 × 10¹¹			0.035 μs	41
CsPb_0.5Sn_0.5I₃ (5% (PEA)₂Pb_0.5Sn_0.5I₄)	700~900	270 @850 nm	5.42×10¹⁴				42
MA_0.5FA_0.5Pb_0.5Sn_0.5I₃(2.5% (PEA)₂Pb_0.5Sn_0.5I₄)	700~900	≈100 @800 nm	≈1.6 × 10¹²	≈14% @800 nm		10 μs /10 μs	51
(MAPbI₃)_0.5(FASnI₃)_0.5	300~1050	410	2.91×10¹²	>60 @808 nm		10.9 ms/8.9 ms	43
MA_0.5FA_0.5Pb_0.5Sn_0.5I₃	350~1000	>200 @ 800~950 nm	>10¹²	≈10% @800 nm			44
MA_0.3FA_0.7Pb_0.5Sn_0.5I₃	470~910	600	1.5 × 10¹²	85% @850 nm			45
FA_0.5MA_0.45Cs_0.05Pb_0.5Sn_0.5I₃	300~1050	350 @950 nm	2.21 × 10¹¹	75% @800 nm	185	42.9 ns	46
Cs_0.15FA_0.85Pb_0.5Sn_0.5I₃	300~1050	520 @850 nm	5.34 × 10¹²	75% @850 nm	224	39.68 ns	47
FA_0.7MA_0.3Sn_0.5Pb_0.5I₃	450~900	510	1.8 × 10¹²	75.4% @840 nm		94 ns/97 ns	48
FA_0.85Cs_0.15Sn_0.5Pb_0.5I₃	400~900	570	8.48 × 10¹²	80 @910 nm		67.5 ns/0.72 μs	49
MASn_0.25Pb_0.75I₃	500~900	510	1.1 × 10¹³		192.6		52

Fig.4 (a) Sample schematic of Sn perovskite NWs[30];(b) Rise/fall time of CsSnI3 perovskite PDs[31];(c)XPS curves of CsSnI3 samples after exposure to air for 6 h[32];(d) SEM images of FASnI3 thin films with and without KHQSA modification[33];(e) Detectivity curves of FASnI3/PEDOT:PSS perovskite PDs [35] Copyright 2016, American Chemical Society. Copyright 2019, American Chemical Society. Copyright 2020, Wiley-VCH. Copyright 2019, Wiley-VCH. Copyright 2020, American Chemical Society.

Fig.5 (a) Band gap of MASnxPb1-xI3 perovskite films (0 < x < 1)[37] ;(b) XRD images of perovskite films doped with or without rubidium ions[38] ;(c) SEM images of perovskite films at different crystallization times[39];(d) SEM images of (FASnI3)0.6(MAPbI3)0.4 perovskite films with different thicknesses [14];(e) Double-sided passivation of Sn/Pb perovskite PDs EQE spectral curve by PEAI[41] ;(f) Photocurrent and dark current J-V curves of PDs with or without azobenzene derivatives[46] Copyright 2018,Wiley-VCH. Copyright 2018, Wiley-VCH Copyright 2019, American Chemical Society. Copyright 2017, Wiley-VCH. Copyright 2020, Wiley-VCH. Copyright 2021，Elsevier.

Table 2 Common Pb Perovskite NIR-PDs

Perovskite	Wavelength range (nm)	Responsivity (mA·W⁻¹)	Detection rate (Jones)	EQE (%)	LDR (dB)	Response time [trise/tdecay] (µs)	Ref.
MAPbI₃/Gd-doped ZnO nanorods	250~1357	220 @1357 nm	9.3×10⁹@1357 nm			4 × 10⁵ /5 × 10⁵	17
MAPbI_3-xCl_x		10¹² @1100 nm	5.6 × 10¹³ @895 nm				18
MAPbI₃	400~1064	150 @820 nm		22% @820 nm		1.2 × 10⁵/8 × 10⁴	21
MAPbI₃	400~1000	4 × 10³@800 nm		600% @800 nm		39/1.9	22
CsPbBr₃/GeSn	450~2200	4.7 @2200 nm				-/26	55
Si/MAPbBr₃ single crystal	405~1064	5 @1064 nm	2×10¹⁰@1064 nm			0.52/2.44	56
MAPbI₃/Si-NPA	400~1050	8.13 @780 nm	9.74 × 10¹² @780 nm			253.3/230.4	57
MAPbI_3-x(SCN)_x/Si-NWs	350~1100	1.3 × 10⁴ @800 nm	1.0 × 10¹³ @800 nm			22.2/17.6	58
Cs-doped FAPbI₃/Si nanowire array	300~1200	14.86 @850 nm	2.04 × 10¹⁰ @850 nm			4/8	59
PVP-modified MAPbI_xCl_3-x/Si	405~988	≈1250 @988 nm	≈5.3 × 10¹¹ @808 nm	≈275% @808 nm	44	645/560	60
Si/MAPbI₃	300~1150	50.9 @815 nm	2.23 × 10¹² @815 nm	<10%		1.3×10⁴/1.46× 10⁴	61
MAPbI_xCl_3-x/Si	300~1150	870 @800 nm	6 × 10¹²@800 nm			5×10⁴ /1.5×10⁵	62
MAPbI₃/Si	400~1200	18.4 @970 nm	1.8 × 10¹²@970 nm	23.5%			97
graphene/CH₃NH₃PbI₃	400~800	180	>10¹⁵	5×10⁴%		87 ms/540 ms	63
(PEA)₂(MA)₂Pb₃I₁₀/GaAs NWs	400~800	75	1.49×10¹¹			568 ms/785 ms	74
FA_0.85Cs_0.15PbI₃/PtSe₂	300~1200	117.7 @808 nm	2.91 × 10¹² @808 nm	14.9% @808 nm		0.078/0.060	68
FA_0.85Cs_0.15PbI₃/PtSe₂	200~1550	313 @808 nm	2.72 × 10¹³ @808 nm	50% @808 nm		3.5/4	69
MAPbI₃/MoS₂	500~850	1.11×10⁵ @850 nm	2.39 × 10¹⁰@850 nm			6.17×10⁶/4.5× 10⁶	71
graphene /(PEA)₂SnI₄/MoS₂/ graphene	300~900	121	8.09 × 10⁹	38.2		34 ms/38 ms	70
MAPbI₃/PbS QDs layer	375~1100	132 @900 nm	5.1 × 10¹² @900 nm	18.2% @900 nm	100		80
MAPbI₃/PbS-SCN QDs layer	365~1550	1.58×10³@940 nm	3.0 × 10¹¹@940 nm			<4.2×10⁴	81
MAPbI₃:PbS QDs	400~1000		3.30 × 10¹¹@900 nm	6% @900 nm		<5 × 10⁵	83
MAPbI_2.5Br_0.5PbS QDs	400~1400	99 @975	4 ×10¹² @1240 nm	40% @1240 nm	60	<10	79
MAPbI₃/PbSe QDs layer	300~1500	700 @1200 nm	7×10⁷@1200 nm			2.5×10³/3×10³	82
MAPbI_3-xCl_x:PbS QDs	300~1500	350 @1300 nm	9 × 10¹⁰@1300			250/500	98
MAPbI₃/PDPP3T	300~940	154 @835 nm	8.8 × 10¹⁰ @835 nm	1% @937 nm		3×10⁴/1.5×10⁵	88
MAPbI₃/PDPPTDTPT	350~1050	1 × 10¹¹@900 nm	10%~20% @800~950 nm		95	6.1 × 10⁻³	89
MAPbI₃/PTB7-Th/IEICO-4F	340~940	518	>10¹⁰@340~940 nm	>70%		500/510	92
MAPbI₃/SWCNTs/NDI-DPP	375~1400	150 @1064 nm	2×10¹²@920~940 nm	20% @920~940 nm		4.32/12.16	93
MAPbI₃/F8IC:PTB7-Th	300~1000	370 @870 nm	2.3 × 10¹¹@870 nm	54% @850 nm	191	35/20	94

Table 2 Common Pb Perovskite NIR-PDs

Perovskite	Wavelength range (nm)	Responsivity (mA·W⁻¹)	Detection rate (Jones)	EQE (%)	LDR (dB)	Response time [trise/tdecay] (µs)	Ref.
MAPbI₃/Gd-doped ZnO nanorods	250~1357	220 @1357 nm	9.3×10⁹@1357 nm			4 × 10⁵ /5 × 10⁵	17
MAPbI_3-xCl_x		10¹² @1100 nm	5.6 × 10¹³ @895 nm				18
MAPbI₃	400~1064	150 @820 nm		22% @820 nm		1.2 × 10⁵/8 × 10⁴	21
MAPbI₃	400~1000	4 × 10³@800 nm		600% @800 nm		39/1.9	22
CsPbBr₃/GeSn	450~2200	4.7 @2200 nm				-/26	55
Si/MAPbBr₃ single crystal	405~1064	5 @1064 nm	2×10¹⁰@1064 nm			0.52/2.44	56
MAPbI₃/Si-NPA	400~1050	8.13 @780 nm	9.74 × 10¹² @780 nm			253.3/230.4	57
MAPbI_3-x(SCN)_x/Si-NWs	350~1100	1.3 × 10⁴ @800 nm	1.0 × 10¹³ @800 nm			22.2/17.6	58
Cs-doped FAPbI₃/Si nanowire array	300~1200	14.86 @850 nm	2.04 × 10¹⁰ @850 nm			4/8	59
PVP-modified MAPbI_xCl_3-x/Si	405~988	≈1250 @988 nm	≈5.3 × 10¹¹ @808 nm	≈275% @808 nm	44	645/560	60
Si/MAPbI₃	300~1150	50.9 @815 nm	2.23 × 10¹² @815 nm	<10%		1.3×10⁴/1.46× 10⁴	61
MAPbI_xCl_3-x/Si	300~1150	870 @800 nm	6 × 10¹²@800 nm			5×10⁴ /1.5×10⁵	62
MAPbI₃/Si	400~1200	18.4 @970 nm	1.8 × 10¹²@970 nm	23.5%			97
graphene/CH₃NH₃PbI₃	400~800	180	>10¹⁵	5×10⁴%		87 ms/540 ms	63
(PEA)₂(MA)₂Pb₃I₁₀/GaAs NWs	400~800	75	1.49×10¹¹			568 ms/785 ms	74
FA_0.85Cs_0.15PbI₃/PtSe₂	300~1200	117.7 @808 nm	2.91 × 10¹² @808 nm	14.9% @808 nm		0.078/0.060	68
FA_0.85Cs_0.15PbI₃/PtSe₂	200~1550	313 @808 nm	2.72 × 10¹³ @808 nm	50% @808 nm		3.5/4	69
MAPbI₃/MoS₂	500~850	1.11×10⁵ @850 nm	2.39 × 10¹⁰@850 nm			6.17×10⁶/4.5× 10⁶	71
graphene /(PEA)₂SnI₄/MoS₂/ graphene	300~900	121	8.09 × 10⁹	38.2		34 ms/38 ms	70
MAPbI₃/PbS QDs layer	375~1100	132 @900 nm	5.1 × 10¹² @900 nm	18.2% @900 nm	100		80
MAPbI₃/PbS-SCN QDs layer	365~1550	1.58×10³@940 nm	3.0 × 10¹¹@940 nm			<4.2×10⁴	81
MAPbI₃:PbS QDs	400~1000		3.30 × 10¹¹@900 nm	6% @900 nm		<5 × 10⁵	83
MAPbI_2.5Br_0.5PbS QDs	400~1400	99 @975	4 ×10¹² @1240 nm	40% @1240 nm	60	<10	79
MAPbI₃/PbSe QDs layer	300~1500	700 @1200 nm	7×10⁷@1200 nm			2.5×10³/3×10³	82
MAPbI_3-xCl_x:PbS QDs	300~1500	350 @1300 nm	9 × 10¹⁰@1300			250/500	98
MAPbI₃/PDPP3T	300~940	154 @835 nm	8.8 × 10¹⁰ @835 nm	1% @937 nm		3×10⁴/1.5×10⁵	88
MAPbI₃/PDPPTDTPT	350~1050	1 × 10¹¹@900 nm	10%~20% @800~950 nm		95	6.1 × 10⁻³	89
MAPbI₃/PTB7-Th/IEICO-4F	340~940	518	>10¹⁰@340~940 nm	>70%		500/510	92
MAPbI₃/SWCNTs/NDI-DPP	375~1400	150 @1064 nm	2×10¹²@920~940 nm	20% @920~940 nm		4.32/12.16	93
MAPbI₃/F8IC:PTB7-Th	300~1000	370 @870 nm	2.3 × 10¹¹@870 nm	54% @850 nm	191	35/20	94

Fig.6 (a) SEM images of Si-NPA substrate covered with perovskite layer[57];(b) The ascending and descending curves of MAPbI3/Si-NW heterojunction device[58]; (c) diagram of Si/SnO2 /MAPbI3/MoO3 heterojunction energy bands [61] Copyright 2019,Elsevier. Copyright 2021, Wiley-VCH. Copyright 2020, The Japan Society of Applied Physics.

Fig.7 (a) Wavelength responsiveness and detection of PtSe2/ perovskite heterojunction PDs[68]; (b) The photocurrent of PdSe2/perovskite heterojunction PDs varies as a function of different polarization angles[69] Copyright 2018, American Chemical Society. Copyright 2019, Wiley-VCH.

Fig9 (a) Schematic diagram of manufacturing flexible PDs using MAPbI3/PDPP3T composite photosensitive layer[88]; (b) EQE and TPC of perovskite /PDPPTDTPT/PC61BM composite PDs[89]; (c) Perovskite /PC61BM/C60 PDs dark current density-voltage (J-V) image[90]; (d) The dual-electron transport layer IEICO-4F and PTB7-Th PDs band map are introduced[92]; (e) detectivity versus wavelength of introduced NDI-DPP/perovskite PDs[93]. Copyright 2016, Wiley-VCH. Copyright 2017, Royal Society of Chemistry. Copyright 2015, Wiley-VCH. Copyright 2018, Wiley-VCH. Copyright 2017, Wiley-VCH.

Fig.8 The structural formula of (a) PDPP3T[88]; (b) PDPPTDTPT[89]; (c) F8IC[94]; (d) PTB7-Th[92]; (e) IEICO-4F[92]; (f) NDI-DPP[93]; which are adopted to combine with perovskite to broaden the spectral response range of Pb perovskite-based PDs.

Fig10 (a) Design and demonstration of a PbS-SCN/MAPbI3 photodetector array for image-sensing application[81] ;(b) Schematic of the image scanning system and actual imaging for the OIHP photodetector[99] ;(c) Schematic diagram of the NIR up-conversion detection system with pictures of experimental detection under weak light and darkness to avoid the effects of indoor lighting[41] ;(d) Schematic diagram of the integrated NIR acousto-optic communication system with mixed perovskite photodetector[46] ;(e) Photocurrent distribution and capture images of 6 × 6 pixel Sn/Pb chalcogenide devices[39] Copyright 2019,American Chemical Society. Copyright 2020, Nature. Copyright 2020, Wiley-VCH. Copyright 2021，Elsevier. Copyright 2021, American Chemical Society.

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Perovskite-Based Near-Infrared Photodetectors

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Perovskite-Based Near-Infrared Photodetectors