Photomultiplication Type Research Articles

Adopting Buffer Layer for Improving Signal‐to‐Noise Ratio of Broadband Photomultiplication Type Organic Photodetectors

AbstractThe photomultiplication type organic photodetectors (PM‐OPDs) are prepared with structure of ITO/PNDIT‐F3N/F8BT/Y6‐1O:P3HT (100:3, wt/wt)/Al, containing hole traps formed with P3HT surrounded by Y6‐1O in active layers. The PM‐OPDs exhibit external quantum efficiency (EQE)>100% in the spectral response range from 310 to 910 nm, resulting from electron tunneling injection assisted by trapped hole near ITO electrode. The incorporation of F8BT buffer layers can induce the markedly decreased dark current density (JD) due to the large electron injection barrier. The light current density (JL) of PM‐OPDs exhibits slightly decreased by inserting F8BT buffer layers due to the enhanced electron tunneling injection assisted by the more trapped holes near ITO electrode. The signal‐to‐noise ratio (SNR) of PM‐OPDs achieves over 40‐fold increment by inserting appropriate thickness of F8BT buffer layers, resulting from the markedly decreased JD and reasonably high JL. The optimal PM‐OPDs exhibit excellent photodetection capability with EQE of 4200% at 360 nm and 6600% at 850 nm, associated with the specific detectivity of 3.9 × 1011 Jones at 360 nm and 9.7 × 1011 Jones at 850 nm.

Recent Advances in Organic Photodetectors

Organic photodetectors (OPDs) have garnered significant attention in fields such as image sensing, health monitoring, and wearable devices due to their exceptional performance. This review summarizes recent research advancements in materials, structures, performance, and applications of narrowband organic photodetectors, hybrid organic–inorganic perovskite photodetectors, flexible organic photodetectors (FOPDs), and photomultiplication type organic photodetectors (PM-OPDs). Organic semiconductors offer substantial potential in optoelectronic devices owing to their low cost, ease of processing, and tunable spectral response. Hybrid perovskite materials extend the spectral response range, FOPDs meet the demands of wearable devices, and PM-OPDs enhance sensitivity, allowing for the detection of weak light signals. Through innovations in materials, structural optimization, and improvements in manufacturing processes, the performance of OPDs has seen significant enhancement. This article also explores the application prospects of these technologies in medical monitoring, optical communications, and image sensing.

High-Sensitivity and Fast-Response Photomultiplication Type Photodetectors Based on Quasi-2D Perovskite Films for Weak-Light Detection.

Photovoltaic photodiodes often face challenges in effectively harvesting electrical signals, especially when detecting faint light. In contrast, photomultiplication type photodetectors (PM-PDs) are renowned for their exceptional sensitivity to weak signals. Here, an advanced PM-PD is introduced based on quasi 2D Ruddlesden-Popper (Q-2D RP) perovskites, optimized for weak light detection at minimal operating voltages. The abundant traps at the Q-2D RP surface capture charge carriers, inducing a trap-assisted tunneling mechanism that leads to the photomultiplication (PM) effect. Deep-lying trap states within the Q-2D RP bulk accelerate charge carrier recombination, resulting in an outstanding rise/fall time of 1.14/1.72 µs for the PM-PDs. The PM-PD achieves a remarkable response level of up to 45.89 AW-1 and an extraordinary external quantum efficiency of 14400% at -1V under an illumination of 1 µWcm- 2. The intrinsic high resistance of the Q-2D perovskite results in a low dark current, enabling an impressive detectivity of 4.23 × 1012 Jones based on noise current at -1V. Furthermore, the practical application of PM-PDs has been demonstrated in weak-light, high-rate communication systems. These findings confirm the significant potential of PM-PDs based on Q-2D perovskites for weak light detection and suggest new directions for developing low-power, high-performance PM-PDs for future applications.

Narrowband Organic Photodetectors: From Fundamentals to Prospects

AbstractOrganic photodetectors (OPDs) have achieved rapid development due to the emergence of organic semiconducting materials with high absorption coefficient and tunable optical bandgap, as well as the progress in device physics and engineering. The working mechanism and fundamental parameters of OPDs are briefly introduced. Some smart strategies for realizing high performance photovoltaic type narrowband OPDs (PV‐NB‐OPDs) and photomultiplication type narrowband OPDs (PM‐NB‐OPDs) are comprehensively reviewed. The recent progress of PV‐NB‐OPDs and PM‐NB‐OPDs is systematically introduced from fundamentals to prospects, exhibiting colorful development and application potential in full‐color imaging, spectroscopic photodetection, medical monitoring, and optical communication, which may promote their rapid development for the potential applications.

Photomultiplication type quasi-planar all-polymer photodetectors with tunable response range

Photomultiplication type quasi-planar all-polymer photodetectors (PM-QAPDs) are fabricated with P3HT/PY-IT as active layers by employing a sequential spin-coating method. The part of PY-IT can penetrate into a P3HT layer to emerge isolated electron-traps formed with PY-IT surrounded by P3HT. The trapped electron distribution near an Al electrode will determine the spectral response range of PM-QAPDs. Broadband PM-QAPDs can be achieved with a 0.25 μm thick P3HT layer and a ultra-thin PY-IT layer prepared from 1 mg/ml solution, exhibiting a broad response from 320 to 870 nm. An external quantum efficiency (EQE) value of optimal PM-QAPDs approaches 16 000% at 360 nm under −12 V bias. When the thickness of the P3HT layer is increased to 2.4 μm, the PM-QAPDs exhibit a narrowband response from 630 to 870 nm, which can be well explained according to the Beer–Lambert law. The work may provide a smart strategy to adjust response range of PM-QAPDs by alerting the thickness of the donor layer.

Photomultiplication type inverted organic photodetector based on PbS quantum dots

In this paper, we report an electron injection photomultiplication (PM) type inverted organic photodetector (OPD) based on [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b’]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT), poly(3-hexylthiophene) (P3HT) and PbS quantum dots (QDs). The effects of PbS QDs added to PCPDTBT: P3HT on the optical and electrical properties of OPDs were investigated. It is found that when the mass ratio of PbS QDs is 5 wt%, the responsivity (R) and external quantum efficiency (EQE) of the device reach 15.3 A/W and 365% at −2 V bias and 430 nm illumination, respectively. The results show that PbS QDs can act as hole traps in the active layer to introduce a large amount of electron injection from the anode circuit, thereby increasing the photocurrent and realizing the PM phenomenon. However, too much doping will cause the trap material to agglomerate and fail, losing the multiplier effect. It provides a theoretical basis and method for high response polyphase inverted PM type OPDs.

CuBi2O4nanocrystals integrated with polyaniline nanobelt arrays for weak light photomultiplication type photodetector

Novel CuBi2O4nanocrystals incorporated in the polyaniline matrix utilized for the fabrication of a flexible and bio-compatible device for the detection of low-intensity photons by using a photomultiplication type photodetector.

Highly Sensitive Dual‐Band Switchable between Ultraviolet and Visible Region Photomultiplication Type Polymer Photodetectors

AbstractDual‐band photomultiplication type polymer photodetectors (PM‐PPDs) are achieved with the structure of ITO/PDIN/poly[N,N′‐bis(4‐butylphenyl)‐N,N′‐bis(phenyl)benzidine] (poly‐TPD):2,2′‐((2Z,2′Z‐(12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2′′,3′′:4′,5′]thieno‐[2′,3′:4,5] pyrrolo‐[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis‐(methanylylidene)) bis‐(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))‐dimalononitrile (Y6) (100:2, wt/wt)/MoO3/poly(3‐hexylthiophene) (P3HT):[6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) (100:2, wt/wt)/Al. Electron traps can be formed with Y6 surrounded by poly‐TPD or with PC71BM surrounded by P3HT. Trapped electrons near ITO/PDIN or Al electrode can assist hole tunneling injectionunder forward or reverse bias, respectively. The dual‐band PM‐PPDs exhibit ultraviolet spectral response under forward bias dependent on trapped electron distribution near ITO/PDIN electrode, while presenting visible spectral response under reverse bias determined by trapped electron distribution near Al electrode. The performance of dual‐band PM‐PPDs can be optimized by decreasing P3HT:PC71BM layer thickness. The optimal dual‐band PM‐PPDs exhibit external quantum efficiency (EQE) of 2800% at 350 nm under +10 V bias with full‐width at half‐maximum of 80 nm, while achieving EQE of 7500% at 430 nm under −10 V bias. The EQE values of optimal dual‐band PM‐PPDs are markedly improved by raising bias, reaching 13 000% at 350 nm under +16 V bias and 27 000% at 430 nm under −16 V bias. This work provides an effective method to prepare dual‐band PM‐PPDs by manipulating the interfacial trapped electron distribution.

Development of Air‐Stable Photomultiplication‐Type Organic Photodetector and Analysis of Active Layer using Removable Top Electrode (Adv. Electron. Mater. 11/2022)

Photomultiplication Type Organic Photodetector with Removable Top Electrode In article number 2200651, Takao Someya, Tomoyuki Yokota, and co-workers develop airstable photomultiplication type organic photodetector with removable top electrode. The developed structure enables the direct and continuous analysis of the active layer after operation in air.

Photomultiplication type organic photodetectors with different response characteristics under forward or reverse bias

Photomultiplication type organic photodetectors (PM-OPDs) with a sandwich structure of ITO/PNDIT-F3N/P3HT:[71]PCBM(100:1, wt/wt)/Al were successfully developed, exhibiting different response characteristics under forward or reverse bias. The rather less [71]PCBM can act as isolated electron traps to capture photogenerated electrons. The trapped electrons near ITO (Al) electrode can make interfacial band bending for hole tunneling injection from external circuit under forward (reverse) bias. The injected holes can be efficiently transported along the channel provided by P3HT and then collected by the corresponding electrode under bias. The external quantum efficiency (EQE) spectral shape of PM-OPDs is primarily determined by the trapped electron distributions near ITO or Al electrode under forward or reverse bias. The PM-OPDs exhibit flat EQE spectra under forward bias and ‘M-shaped’ EQE spectra under reverse bias, which is consistent with the curves of trapped electron distribution near ITO or Al electrode. The champion EQE values of PM-OPDs arrive to 2550% at 425 nm under 10 V bias and 2360% at 365 nm under −10 V bias. The PM-OPDs exhibit distinct response speed under forward or reverse bias, which is primarily attributed to the different trapped electron density near ITO or Al electrode under incident light from ITO side. • The PNDIT-F3N interfacial layer makes PM-OPDs work well under forward or reverse bias. • The response speed of PM-OPDs was investigated under distinct polarity bias, resulting from trapped electrons near electrode. • The champion EQE values of PM-OPDs arrive to 2550% at 425 nm under 10 V bias and 2360% at 365 nm under −10 V bias.

Ultraviolet Narrowband Photomultiplication Type Organic Photodetectors with Fabry−Pérot Resonator Architecture

AbstractUltraviolet (UV) narrowband photodetectors play a critical role in missile detection, flame monitoring, optical communication, etc. It is a great challenge to realize UV narrowband organic photodetectors due to wide photo‐harvesting property of organic materials, especially for photomultiplication type organic photodetectors (PM‐OPDs). In this work, a smart strategy is proposed to achieve UV narrowband response by coupling Fabry−Pérot microcavity with PM‐OPDs. PM‐OPDs are realized by using poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C71‐butyric acid methyl ester (100:1, w/w) as active layers, exhibiting broadband response range covering from UV–vis region. Series of optical microcavities consisting of Ag/LiF/Ag with UV spectral selectivity are prepared, which are employed to couple with the PM‐OPDs for achieving UV narrowband response. The UV spectral selectivity of optical microcavity can be optimized by tuning the thickness of spacer layer and mirror layers, which can further regulate the photogenerated electron distribution near Al electrode to optimize the external quantum efficiency (EQE) spectra of the PM‐OPDs coupled with optical microcavity. The optimized PM‐OPDs coupled with optical microcavity exhibit EQE of 9300% at 350 nm and narrowband response with 33 nm full‐width at half‐maximum under −15 V bias. This work indicates that PM‐OPDs coupled with optical microcavity should be an efficient strategy for achieving UV narrowband response.

Highly sensitive photomultiplication type polymer photodetectors by manipulating interfacial trapped electron density

Photomultiplication type polymer photodetectors (PM-PPDs) are successfully achieved via interfacial trap-assisted hole tunneling injection from external circuit. The external quantum efficiency (EQE) of PM-PPDs is mainly determined by the number of injected holes from external circuit and flowing across the devices. Although the trapped electron density near Al electrode can be increased for efficient hole tunneling injection by decreasing the thickness of active layers, which also makes the PM-PPDs vulnerable to breakdown. A smart strategy is firstly proposed to obtain large EQE values by decreasing the thickness of active layers and keep excellent withstanding large bias characteristic of PM-PPDs by using wide bandgap polymer poly-TPD as buffer layer. The optimal double layered ternary PM-PPDs were obtained with 40 nm poly-TPD as buffer layer and 90 nm P3HT:PBDB-T:PC61BM (80:20:2, wt/wt/wt) as active layers, exhibiting a rather large EQE value of 21400% and specific detectivity of 1.0 × 1013 Jones at 430 nm under −8 V bias. This work indicates that inserting wide bandgap and high hole mobility material as buffer layer should be an efficient strategy to prepare highly sensitive PM-PPDs, benefiting from the increased hole tunneling injection from external circuit and efficient hole flowing across the devices.

Highly sensitive broadband photomultiplication type all-polymer photodetectors and their applications in optical pulse counting

Broadband photomultiplication type all-polymer photodetectors with the structure of ITO/PFN-Br/PBDB-T : PYF-T-o (3 : 100)/LiF/Au achieve EQEs of 18 000% at 360 nm and 9000% at 850 nm under 4 V, which are applied in an optical pulse counting circuit.

Employing liquid crystal material as regulator to enhance performance of photomultiplication type polymer photodetectors

Photomultiplication type polymer photodetectors (PM-PPDs) were achieved with PBDB-T:BTPV-4F (98:2, wt/wt) as blend active layer based on a sandwich structure. Isolated electron traps are formed due to the rather less BTPV-4F surrounded by PBDB-T in blend active layers. Trapped electrons in BTPV-4F near Al electrode will induce interfacial band bending for hole tunneling injection into blend active layers. The tunneling injected holes will be transported along the channels formed by PBDB-T in blend active layers, photomultiplication phenomenon will be obtained when the number of holes crossing through blend active layers is larger than that of incident photons per unit time. Liquid crystal material BTR was selected as regulator to adjust PBDB-T molecular arrangement for improving hole mobility in blend active layers, leading to optimized performance of PM-PPDs. Optimal PM-PPDs were obtained with PBDB-T:BTR:BTPV-4F (89:9:2, wt/wt/wt) as blend active layer. The external quantum efficiency (EQE) values of optimal PM-PPDs are 1.5 times that of PM-PPDs based on PBDB-T:BTPV-4F (98:2, wt/wt) in the whole spectral response range under −10 V applied bias. The EQE of optimal PM-PPDs can be markedly improved by increasing applied bias, which is improved from 600% to 19,300% at 660 nm with applied bias increased from −10 to −20 V. The responsivity of optimal PM-PPDs arrives to 102 A W−1 at 660 nm under −20 V applied bias.

Effective film surface treatment for improving external quantum efficiency of photomultiplication type organic photodetector

A simple yet effective method based on methanol treatment is proposed to enhance the external quantum efficiency (EQE) of the photomultiplication type organic photodetector with a structure of Glass/ITO/PEDOT:PSS/P3H:PC71BM (100:1, wt./wt.)/Al. By modifying the PEDOT:PSS film surface with methanol, the EQE of photodetector significantly improved within a broad wavelength range of 300–700 nm. The maximum EQE of 25300% occurs at the wavelength of 350 nm in the methanol-treated device under −9 V bias, which more than doubles that (11500%) of the device without treatment. In addition, as a result of the methanol treatment, the detectivity of the device improved from 3.72 × 1012 to 7.24 × 1012 Jones at −9 V under 350 nm light illumination. The large improvement is attributed to the fact that the methanol treatment can improve the electrical performance of the PEDOT:PSS by removing the insulator PSS within the film and also result in PC71BM aggregations in the active layer. The latter can enhance the tunneling hole injection by the intensified energy-level bending, which is induced by both the trapped electrons in these aggregations and accumulated ones near Al electrode. As a result, the modification of both the PEDOT:PSS layer and the active layer increases the response current, resulting in the EQE improvement.

Highly sensitive all-polymer photodetectors with ultraviolet-visible to near-infrared photo-detection and their application as an optical switch

All-polymer photomultiplication type photodetectors were built based on PMBBDT:N2200 (100 : 3, w/w) as photoactive layers, which can be applied in optical switch systems without any current pre-amplifier.

Broadband photomultiplication organic photodetectors.

Broadband photomultiplication organic photodetectors (PMOPDs) can be achieved with a double-layered active layer prepared from IEICO-4F : PBDB-T blend solutions with different weight ratios (1 : 1 or 3 : 100, wt/wt). The response range of the double-layered PMOPDs covers from 310 nm to 930 nm, determined by the photon harvesting range of the IEICO-4F : PBDB-T (1 : 1, wt/wt) layer. The IEICO-4F : PBDB-T (3 : 100, wt/wt) layer was used as a PM layer in the double-layered PMOPDs, achieving external quantum efficiency (EQE) more than 100% based on the work mechanism of trap-assisted hole tunneling injection. The trapped electrons in PBDB-T/IEICO-4F/PBDB-T near the Al electrode will makeinterfacial-band-bending to narrow the injection barrier, resulting in hole-tunneling-injection from the external circuit. The polymer PBDB-T can provide an efficient charge transport channel for the injected hole from the external circuit. The specific detectivity (D*) and responsivity (R) of the double-layered PMOPDs are 1.05 ± 0.03 × 1012 Jones and 0.94 ± 0.03 A W-1 at 810 nm under a -10 V bias, respectively.

End‐Group Functionalization of Non‐Fullerene Acceptors for High External Quantum Efficiency over 150 000% in Photomultiplication Type Organic Photodetectors

AbstractPhotomultiplication‐type organic photodetectors (PM‐OPDs) with high external quantum efficiency (EQE) of over 100% are attracting increasing attention due to their potential importance in detecting weak incident light. Considering that the gain of PM‐OPD is determined by the ratio of carrier lifetime over carrier transit time, a systematic study on the effect of the end‐functionalization of a new extended aromatic fused‐ring non‐fullerene acceptor (NFA) on the carrier trap/transit time of the PM‐OPD. Photophysical analyses by means of ultraviolet‐visible absorption, ultraviolet photoelectron spectroscopy, and photoluminescence combined with structural analyses through grazing‐incidence wide‐angle X‐ray scattering show that fluorination of the NFA with the deepest lowest unoccupied molecular orbital level and non‐isotropic molecular ordering can yield the longest carrier lifetime. Furthermore, surface energy study show that fluorination of the NFA can also yield the most hydrophobic nature, which can allow the most efficient injection barrier thinning/lowering of the active layer/cathode interface under illumination due to the localized acceptor distribution toward cathode, maximizing the hole injection efficiency from cathode. As a result, an unprecedentedly high EQE of 156 000% is obtained from the optimized PM‐OPD. This work shows the importance of the molecular design of acceptor molecules in fabricating high‐performance PM‐OPDs.

Photomultiplication type near‐infrared organic photodetectors with a mixed active layer

AbstractPhotomultiplication type near‐infrared (NIR) organic photodetectors (OPDs) are constructed with lead phthalocyanine (PbPc) and C60 acted as the donor and acceptor, respectively. Compared with the PbPc/C60 planar heterojunction device, the PbPc:C60 mixed active layer devices show enhanced NIR responses. The optimized mixed active layer device displays an external quantum efficiency (EQE) of 22.8% at 870 nm under zero bias, which is about 45% higher than that of planar heterojunction device. Moreover, it also presents a detectivity in the order of 1012 Jones and an EQE of 400% under applied bias of −8 V, indicating a photocurrent gain obtained in the device. Although the mixed active layer devices have a lower absorption in the NIR region, the donor: acceptor mixed structure increases the donor/acceptor contact area and forms continuous carrier transport paths, which increases the excitons dissociation efficiency and the photogenerated carriers collection efficiency and hence the response of the devices.

Photodetectors based on solution-processable semiconductors: Recent advances and perspectives

The detection of light, one of the most important technologies, has widespread applications in industry and our daily life, e.g., environmental monitoring, communications, surveillance, image sensors, and advanced diagnosis. Along with the remarkable progress in the field of organics, those based on quantum dots, and recently emerged perovskite optoelectronics, photodetectors based on these solution-processable semiconductors have shown unprecedented success. In this review, we present the basic operation mechanism and the characterization of the performance metrics based on these novel materials systems. Then, we focus on the current research status and recent advances with the following five aspects: (i) spectral tunability, (ii) cavity enhanced photodetectors, (iii) photomultiplication type photodetectors, (iv) sensitized phototransistors, and (v) ionizing radiation detection. At the end, we discuss the key challenges facing these novel photodetectors toward manufacture and viable applications. We also point out the opportunities, which are promising to explore and may require more research activities.