Colloidal Quantum Dot Photodetectors Research Articles

Assessing the Potential and Limitations of PbS and HgTe Colloidal Quantum Dot Infrared Detectors for Free Space Optical Communication

AbstractFree space optical communication with infrared light is a promising secure wireless optical communication technology, where infrared photodetectors are the core component. To date, such applications are based on epitaxial growth narrow‐band semiconductors facing the challenge of large‐area fabrication. Infrared colloidal quantum dots (CQDs) are of interest because of the high‐throughput solution processing. Here, large‐area CQD photodetectors with adjustable wavelengths covering 1.3–2.0 µm. For 1 × 1 mm2 CQD photodetector, the response time achieved within 1 µs at room temperature, responded sharply to the 25 kbps PRBS‐7 communication code is demonstrated. For 1.5 × 1.5 cm2 large‐area CQD photodetectors, a communication rate of 2 kbps is achieved. This work is a step toward the CQD application in the field of optical communications.

High-Performance Visible to Mid-Infrared Photodetectors Based on HgTe Colloidal Quantum Dots under Room Temperature.

HgTe colloidal quantum dots (CQDs) are one of few materials that can realize near-to-midwave infrared photodetection. And the quality of HgTe CQD directly affects the performance of photodetection. In this work, we optimize the method of synthesizing HgTe CQDs to reduce the defect concentration, therefore improving the photoelectric properties. The photodetector based on HeTe CQD can respond to the light from the visible to mid-infrared band. Notably, a photoresponse to 4000 nm light at room temperature is realized. The responsivity and detectivity are 90.6 mA W-1 and 6.9 × 107 Jones under 1550 nm light illumination, which are better than these of most reported HgTe CQD photodetectors. The response speed reaches a magnitude of microseconds with a rising time of τr = 1.9 μs and a falling time of τf = 1.5 μs at 10 kHz under 1550 nm light illumination.

Dicarboxylic Acid‐Assisted Surface Oxide Removal and Passivation of Indium Antimonide Colloidal Quantum Dots for Short‐Wave Infrared Photodetectors

AbstractHeavy‐metal‐free III–V colloidal quantum dots (CQDs) are promising materials for solution‐processed short‐wave infrared (SWIR) photodetectors. Recent progress in the synthesis of indium antimonide (InSb) CQDs with sizes smaller than the Bohr exciton radius enables quantum‐size effect tuning of the band gap. However, it has been challenging to achieve uniform InSb CQDs with band gaps below 0.9 eV, as well as to control the surface chemistry of these large‐diameter CQDs. This has, to date, limited the development of InSb CQD photodetectors that are sensitive to 1400 nm light. Here we adopt solvent engineering to facilitate a diffusion‐limited growth regime, leading to uniform CQDs with a band gap of 0.89 eV. We then develop a CQD surface reconstruction strategy that employs a dicarboxylic acid to selectively remove the native In/Sb oxides, and enables a carboxylate‐halide co‐passivation with the subsequent halide ligand exchange. We find that this strategy reduces trap density by half compared to controls, and enables electronic coupling among CQDs. Photodetectors made using the tailored CQDs achieve an external quantum efficiency of 25 % at 1400 nm, the highest among III–V CQD photodetectors in this spectral region.

Dicarboxylic Acid-Assisted Surface Oxide Removal and Passivation of Indium Antimonide Colloidal Quantum Dots for Short-Wave Infrared Photodetectors.

Heavy-metal-free III-V colloidal quantum dots (CQDs) are promising materials for solution-processed short-wave infrared (SWIR) photodetectors. Recent progress in the synthesis of indium antimonide (InSb) CQDs with sizes smaller than the Bohr exciton radius enables quantum-size effect tuning of the band gap. However, it has been challenging to achieve uniform InSb CQDs with band gaps below 0.9 eV, as well as to control the surface chemistry of these large-diameter CQDs. This has, to date, limited the development of InSb CQD photodetectors that are sensitive to 1400 nm light. Here we adopt solvent engineering to facilitate a diffusion-limited growth regime, leading to uniform CQDs with a band gap of 0.89 eV. We then develop a CQD surface reconstruction strategy that employs a dicarboxylic acid to selectively remove the native In/Sb oxides, and enables a carboxylate-halide co-passivation with the subsequent halide ligand exchange. We find that this strategy reduces trap density by half compared to controls, and enables electronic coupling among CQDs. Photodetectors made using the tailored CQDs achieve an external quantum efficiency of 25 % at 1400 nm, the highest among III-V CQD photodetectors in this spectral region.

Transient Measurements and Simulations Correlate Exchange Ligand Concentration and Trap States in Colloidal Quantum Dot Photodetectors.

Colloidal quantum dot (CQD) photodetectors (PDs) can detect wavelengths longer than the 1100 nm limit of silicon because of their highly tunable bandgaps. CQD PDs are acutely affected by the ligands that separate adjacent dots in a CQD-solid. Optimizing the exchange solution ligand concentration in the processing steps is crucial to achieving high photodetector performance. However, the complex mix of chemistry and optoelectronics involved in CQD PDs means that the effects of the exchange solution ligand concentration on device physics are poorly understood. Here we report direct correspondence between simulated and experimental transient photocurrent responses in CQD PDs. For both deficient and excess conditions, our model demonstrated the experimental changes to the transient photocurrent aligned with changes in trap state density. Combining transient photoluminescence, absorption, and photocurrent with this simulation model, we revealed that different mechanisms are responsible for the increased trap density induced by excess and deficient active layer ligand concentrations.

Plasmon-enhanced HgTe colloidal quantum dot infrared photodetectors

Surface plasmon resonances based on metal nanoparticles (MNPs) can intensively enhance the electric field strength and capture light in the near-field region, thus greatly improving the performance of photodetectors. Here, we investigate plasmon-enhanced HgTe colloidal quantum dot (CQD) short-wave infrared (SWIR) photodetectors with Ag NPs embedded. Thanks to Ag NPs’ ability to trap the incident light, the light-to-dark current ratio of our enhanced CQD photodetectors with 10 nm Ag NPs is significantly increased by a factor of 5.7. Accordingly, the specific detectivity and responsivity are also enhanced, achieving about 8.92 × 1010 Jones and above 2 AW−1 under 2 V bias, respectively.

Halide-Driven Synthetic Control of InSb Colloidal Quantum Dots Enables Short-Wave Infrared Photodetectors.

In the III-V family of colloidal quantum dot (CQD) semiconductors, InSb promises access to a wider range of infrared wavelengths compared to many light-sensing material candidates. However, achieving the necessary size, size-dispersity, and optical properties has been challenging. Here the synthetic challenges associated with InSb CQDs are investigated and it is found that uncontrolled reduction of the antimony precursor hampers the controlled growth of CQDs. To overcome this, a synthetic strategy that combines nonpyrophoric precursors with zinc halide additives is developed. The experimental and computational studies show that zinc halide additives decelerate the reduction of the antimony precursor, facilitating the growth of more uniformly sized CQDs. It is also found that the halide choice provides additional control over the strength of this effect. The resultant CQDs exhibit well-defined excitonic transitions in spectral range of 1.26-0.98eV, along with strong photoluminescence. By implementing a postsynthesis ligand exchange, colloidally stable inks enabling the fabrication of high-quality CQD films are achieved. The first demonstration of InSb CQD photodetectors is presented reaching 75% external quantum efficiency (QE) at 1200nm, to the knowledge the highest short-wave infrared (SWIR) QE reported among heavy-metal-free infrared CQD-based devices.

Lead Chalcogenide Colloidal Quantum Dots for Infrared Photodetectors.

Infrared detection technology plays an important role in remote sensing, imaging, monitoring, and other fields. So far, most infrared photodetectors are based on InGaAs and HgCdTe materials, which are limited by high fabrication costs, complex production processes, and poor compatibility with silicon-based readout integrated circuits. This hinders the wider application of infrared detection technology. Therefore, reducing the cost of high-performance photodetectors is a research focus. Colloidal quantum dot photodetectors have the advantages of solution processing, low cost, and good compatibility with silicon-based substrates. In this paper, we summarize the recent development of infrared photodetectors based on mainstream lead chalcogenide colloidal quantum dots.

Ultrahigh Detectivity From Multi-Interfaces Engineered Near-Infrared Colloidal Quantum Dot Photodetectors

Low noise ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{i}_{\text{noise}}$</tex-math> </inline-formula> ) and high responsivity ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{R}$</tex-math> </inline-formula> ) are significant factors for Lead sulfide (PbS) colloidal quantum dots (CQDs) photodetectors implementing high specific detectivity ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{D}^\ast$</tex-math> </inline-formula> ). However, the simultaneous achievement of the above two factors is still challenging due to the complicated roles of interfaces and the difficulties in comprehensive interface modification by individual strategy. Here, we propose a well-designed PbS CQD near-infrared (NIR) photodiode with high performance by multi-interface engineering. First, the well-passivated interface of a photo-active layer is obtained by high-quality n-type CQD inks and gentle ligands cross-linked p-type CQD solid films, which leads to low defect density and thus extremely low device dark current ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\sim$</tex-math> </inline-formula> 70 nA <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\cdot$</tex-math> </inline-formula> cm <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{-\text{2}}$</tex-math> </inline-formula> ). Second, the construction of LiF and MoO <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$_{\textit{x}}$</tex-math> </inline-formula> carrier-selective layers in the electrode interfaces greatly increases the photogenerated charge carrier extraction efficiency due to the enhanced built-in electric field, which promotes a high <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{R}$</tex-math> </inline-formula> to 0.61 A <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\cdot$</tex-math> </inline-formula> W <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{-\text{1}}$</tex-math> </inline-formula> at 1100 nm. Both the two modifications enable low <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{i}_{\text{noise}}$</tex-math> </inline-formula> and high <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{R}$</tex-math> </inline-formula> . Hence the device exhibits an ultrahigh <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\textit{D}^\ast$</tex-math> </inline-formula> up to 1.42 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$\times$</tex-math> </inline-formula> 10 <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$^{\text{12}}$</tex-math> </inline-formula> Jones. The further demonstration of high-precision biological health monitoring in both visible and infrared bands by this device illustrates its huge potential in ultra-sensitive broadband optoelectronic applications.

Sequential Co-Passivation in InAs Colloidal Quantum Dot Solids Enables Efficient Near-Infrared Photodetectors.

III-V colloidal quantum dots (CQDs) are promising materials for optoelectronic applications, for they avoid heavy metals while achieving absorption spanning the visible to the infrared (IR). However, the covalent nature of III-V CQDs requires the development of new passivation strategies to fabricate conductive CQD solids for optoelectronics: this work shows herein that ligand exchanges, previously developed in II-VI and IV-VI quantum dots and employing a single ligand, do not fully passivate CQDs, and that this curtails device efficiency. Guided by density functional theory (DFT) simulations, this work develops a co-passivation strategy to fabricate indium arsenide CQD photodetectors, an approach that employs the combination of X-type methyl ammonium acetate (MaAc) and Z-type ligands InBr3 . This approach maintains charge carrier mobility and improves passivation, seen in a 25% decrease in Stokes shift, a fourfold reduction in the rate of first-exciton absorption linewidth broadening over time-under-stress, and leads to a doubling in photoluminescence (PL) lifetime. The resulting devices show 37% external quantum efficiency (EQE) at 950nm, the highest value reported for InAs CQD photodetectors.

Extended wavelength and enhanced sensitivity of PbS colloidal quantum dots/Bi2Te3 photodetector by band alignment engineering

The tunable band gap of PbS colloidal quantum dots (CQDs) from ultraviolet (UV) to short-wave infrared (SWIR) bands provides many potential applications in optoelectronics. However, synthesis of large-sized CQDs that exhibit good stability and sensitivity for extended wavelength still remains a technological challenge. In this paper, a novel broadband photodetector based on small size PbS CQDs (with exciton absorption peak at 927 nm) and Bi2Te3 (with wide spectral sensitivity and high absorption) was developed and studied. The device, which comprised of ITO/AZO/PbS CQDs/Bi2Te3/Al, provided an excellent band alignment that facilitated charge dissociation and transmission hence improving the device sensitivity. Furthermore, wavelength extension was also realized through the synergistic effect of these materials, thus demonstrating broadband photodetection with high sensitivity. The heterostructure photodetector demonstrated good performance in the visible and near infrared ranges, especially at a wavelength of 1050 nm exhibiting a high responsivity (R) and detectivity (D*) of 161 A/W and 3.2 × 1013 Jones, respectively. In addition, the device exhibited excellent stability and reversibility after one month of storage without any encapsulation. This work lays a good foundation for the construction of the next generation of highly sensitive broadband CQDs photodetectors.

Large-area flexible colloidal-quantum-dot infrared photodiodes for photoplethysmogram signal measurements

Epitaxially grown photodiodes are the foundation of infrared photodetection technology; however, their rigid structure and limited area scaling limit their use in advanced applications. Colloidal-quantum-dot (CQD) infrared photodiodes have increased active areas through solution processing, and are thus potential candidates for large-area flexible photodetection, but these large-area photodiodes have disadvantages such as large dark current density, poor homogeneity, and poor stability. Therefore, this study established a fabrication strategy for large-area flexible CQD photodiodes that involves introducing polyimide to CQD ink to improve CQD passivation, monodisperse ink persistence, and film morphology. The resulting CQD photodiodes exhibited reduced dark current density and improved homogeneity and work stability. Furthermore, the as-prepared photodiodes exhibited a detectivity (D*) of greater than 1013 Jones, which was higher than other reported CQD photodetectors. The CQD photodiodes developed in this study can be used for wearable photoplethysmogram (PPG) signal measurement under ambient light at reduced cost and power consumption.

Improvement of Dynamic Performance and Detectivity in Near-Infrared Colloidal Quantum Dot Photodetectors by Incorporating Conjugated Polymers.

Colloidal quantum dots (CQDs) have a unique advantage in realizing near-infrared (NIR) photodetection since their optical properties are readily tuned by the particle size, but CQD-based photodetectors (QPDs) presently show a high dark current density (Jd) and insufficient dynamic characteristics. To overcome these two problems, we synthesized and introduced two types of conjugated polymers (CPs) by replacing the p-type CQD layer in the QPDs. The low dielectric constant and insulating properties of CPs under dark conditions effectively suppressed the Jd in the QPDs. In addition, the energy-level alignment and high-hole mobility of the CPs facilitated hole transport. Therefore, both the responsivity and specific detectivity were highly enhanced in the CP-based QPDs. Notably, the dynamic characteristics of the QPDs, such as the -3 dB cut-off frequency and rising/falling response times, were significantly improved in the CP-based QPDs owing to the sizable molecular ordering and fast hole transport of the CP in the film state as well as the low trap density, well-aligned energy levels, and good interfacial contact in the CP-based devices.

Electron-Transport Layers Employing Strongly Bound Ligands Enhance Stability in Colloidal Quantum Dot Infrared Photodetectors.

Solution-processed photodetectors based on colloidal quantum dots (CQDs) are promising candidates for short-wavelength infrared light sensing applications. Present-day CQD photodetectors employ a CQD active layer sandwiched between carrier-transport layers in which the electron-transport layer (ETL) is composed of metal oxides. Herein, a new class of ETLs is developed using n-type CQDs, finding that these benefit from quantum-size effect tuning of the band energies, as well as from surface ligand engineering. Photodetectors operating at 1450 nm are demonstrated using CQDs with tailored functionalities for each of the transport layers and the active layer. By optimizing the band alignment between the ETL and the active layer, CQD photodetectors that combine a low dark current of ≈1 × 10-3 mA cm-2 with a high external quantum efficiency of ≈66% at 1V are reported, outperforming prior reports of CQD photodetectors operating at >1400 nm that rely on metal oxides as ETLs. It is shown that stable CQD photodetectors rely on well-passivated CQDs: for ETL CQDs, a strongly bound organic ligand trans-4-(trifluoromethyl)cinnamic acid (TFCA) provides improved passivation compared to the weakly bound inorganic ligand tetrabutylammonium iodide (TBAI). TFCA suppresses bias-induced ion migration inside the ETL and improves the operating stability of photodetectors by 50× compared to TBAI.

Passivating {100} Facets of PbS Colloidal Quantum Dots via Perovskite Bridges for Sensitive and Stable Infrared Photodiodes

AbstractSolution‐processed PbS colloidal quantum dots (CQDs) are promising optoelectronic materials for next‐generation infrared imagers due to their monolithic integratability with silicon readout circuit and tunable bandgap controlled by CQDs size. However, large‐size PbS CQDs (diameter &gt;4 nm) for longer shortwave‐infrared photodetection consist mainly of {100} facets with incomplete surface passivation and unsatisfied stability. Here, it is reported that perovskite‐bridged PbS CQDs, in which the {100} facets of the CQDs are epitaxially bridged with CsPbI3–xBrx perovskite, can achieve improved passivation and enhanced stability in comparison with the traditional strategies. The resultant infrared CQDs photodiodes exhibit significantly reduced dark current, nearly 50% enhanced photoresponse, and improved work stability. These superior properties synergistically produce the most balanced performance (with a high −3 dB bandwidth of 42 kHz and an impressive specific detectivity of 6.2 × 1012 Jones) among the reported CQDs photodetectors.

Ultrasensitive Colloidal Quantum-Dot Upconverters for Extended Short-Wave Infrared.

Infrared-to-visible upconverters converting low-energy infrared to higher-energy visible light without bringing in complicated readout integrated circuits have triggered enormous excitement. However, existing upconverters suffer from limited sensing wavelengths, low photon-to-photon (p-p) efficiency, and high minimum detectable infrared power. Here, we reported the colloidal quantum-dot (CQD) upconverters with unprecedented performance. By using HgTe CQDs as the sensing layer, the operation spectral ranges of the upconverters are, for the first time, extended to short-wave infrared. More importantly, the resistance-area products of the HgTe CQD photodetectors are carefully optimized by interface engineering to match with the visible light-emitting diodes so that the quantum efficiency and sensitivity of upconverters can be maximized. The integrated upconverters demonstrate a high p-p efficiency of nearly 30% and a low detection limit down to 20 μW cm-2.

Limiting Factors of Detectivity in Near-Infrared Colloidal Quantum Dot Photodetectors.

Lead sulfide colloidal quantum dots (PbS CQDs) have shown great potential in photodetectors owing to their promising optical properties, especially their strong and tunable absorption. However, the limitation of the specific detectivity (D*) in CQD near-infrared (NIR) photodetectors remains unknown due to the ambiguous noise analysis. Therefore, a clear understanding of the noise current is critically demanded. Here, we elucidate that the noise current is the predominant factor limiting D*, and the noise is highly dependent on the trap densities in halide-passivated PbS films and the carriers injected from the Schottky contact (EDT-passivated PbS films/metal). It is found that the thickness of CQDs is proportional to their interface trap density, while it is inversely proportional to their minimal bulk trap density. A balance point can be reached at a certain thickness (136 nm) to minimize the trap density, giving rise to the improvement of D*. Utilizing thicker PbS-EDT films broadens the width of the tunneling barrier and thereby reduces the carrier injection, contributing to a further enhancement of D*. The limiting factors of D* determined in this work not only explain the physical mechanism of the influence on detection sensitivity but also give guidance to the design of high-performance CQD photodetectors.

Ligand-Engineered HgTe Colloidal Quantum Dot Solids for Infrared Photodetectors.

HgTe colloidal quantum dots (CQDs) are promising absorber systems for infrared detection due to their widely tunable photoresponse in all infrared regions. Up to now, the best-performing HgTe CQD photodetectors have relied on using aggregated CQDs, limiting the device design, uniformity and performance. Herein, we report a ligand-engineered approach that produces well-separated HgTe CQDs. The present strategy first employs strong-binding alkyl thioalcohol ligands to enable the synthesis of well-dispersed HgTe cores, followed by a second growth process and a final postligand modification step enhancing their colloidal stability. We demonstrate highly monodisperse HgTe CQDs in a wide size range, from 4.2 to 15.0 nm with sharp excitonic absorption fully covering short- and midwave infrared regions, together with a record electron mobility of up to 18.4 cm2 V-1 s-1. The photodetectors show a room-temperature detectivity of 3.9 × 1011 jones at a 1.7 μm cutoff absorption edge.

Ambient stability improvement of CQD photodetectors by low-temperature deposited graphene encapsulation

In this work, we have investigated the ambient stability improvement of colloidal quantum dots (CQD) photodetectors by graphene encapsulation. The low temperature deposited graphene is performed to act as an isolating membrane between PbS CQDs and the ambient environment. The oxidization of PbS CQDs can be significantly inhibited with a graphene isolating membrane. In addition, the optoelectronic characteristics of PbS CQDs-based photodetectors encapsulated by graphene are well maintained even exposed in ambient for a month. This work paves the way for the fabrication and application of the air-stable CQDs.

Facet-Oriented Coupling Enables Fast and Sensitive Colloidal Quantum Dot Photodetectors.

Charge carrier transport in colloidal quantum dot (CQD) solids is strongly influenced by coupling among CQDs. The shape of as-synthesized CQDs results in random orientational relationships among facets in CQD solids, and this limits the CQD coupling strength and the resultant performance of optoelectronic devices. Here, colloidal-phase reconstruction of CQD surfaces, which improves facet alignment in CQD solids, is reported. This strategy enables control over CQD faceting and allows demonstration of enhanced coupling in CQD solids. The approach utilizes post-synthetic resurfacing and unites surface passivation and colloidal stability with a propensity for dots to couple via (100):(100) facets, enabling increased hole mobility. Experimentally, the CQD solids exhibit a 10× increase in measured hole mobility compared to control CQD solids, and enable photodiodes (PDs) exhibiting 70% external quantum efficiency (vs 45% for control devices) and specific detectivity, D*>1012 Jones, each at 1550nm. The photodetectors feature a 7ns response time for a 0.01mm2 area-the fastest reported for solution-processed short-wavelength infrared PDs.