Road Map for Nanocrystal Based Infrared Photodetectors

Infrared (IR) sensors based on epitaxially grown semiconductors face two main challenges which are their prohibitive cost and the difficulty to rise the operating temperature. The quest for alternative technologies which will tackle these two difficulties requires the development of new IR active materials. Over the past decade, significant progresses have been achieved. In this perspective, we summarize the current state of the art relative to nanocrystal based IR sensing and stress the main materials, devices and industrial challenges which will have to be addressed over the 5 next years

Field effect transistor and photo transistor of narrow band gap nanocrystal arrays using ionic glasses

International audienceGating of nanocrystal films is currently driven by two approaches: either the use of a dielectric such as SiO2 or the use of electrolyte. SiO2 allows fast bias sweeping over a broad range of temperatures but requires a large operating bias. Electrolyte, thanks to a large capacitance, leads to significantly reduce operating bias but is limited to slow speed and quasi room temperature operation. None of these operating conditions are optimal for narrow band gap nanocrystal-based phototransistors for which the need of a large capacitance gate has to be combined with low temperature operation. Here we explore the use of a LaF3 ionic glass as a high capacitance gating alternative. We demonstrate for the first time the use of such ionic glasses to gate thin films made of HgTe and PbS nanocrystals. This gating strategy allows operation in the 180 to 300 K range of temperatures with capacitance as high as 1 µF·cm-2. We unveil the unique property of ionic glass gate to enable unprecedented tunability of both magnitude and dynamics of the photocurrent, thanks to high charge doping capability within an operating temperature window relevant for infrared photodetection. We demonstrate that by carefully choosing the operating gate bias, the signal to noise ratio can be improved by a factor 100 and the time response accelerated by a factor 6. Moreover, the good transparency of LaF3 substrate allows back side illumination in the infrared which is highly valuable for the design of phototransistor

Transport and Phototransport in ITO Nanocrystals with Short to Long-Wave Infrared Absorption

Nanocrystals are often described as an interesting strategy for the design of low-cost optoelectronic devices especially in the infrared range. However the driving materials reaching infrared absorption are generally heavy metalcontaining (Pb and Hg) with a high toxicity. An alternative strategy to achieve infrared transition is the use of doped semiconductors presenting intraband or plasmonic transition in the short, mid and long-wave infrared. This strategy may offer more flexibility regarding the range of possible candidate materials. In particular, significant progresses have been achieved for the synthesis of doped oxides and for the control of their doping magnitude. Among them, tin doped indium oxide (ITO) is the one providing the broadest spectral tunability. Here we test the potential of such ITO nanoparticles for photoconduction in the infrared. We demonstrate that In2O3 nanoparticles presents an intraband absorption in the mid infrared range which is transformed into a plasmonic feature as doping is introduced. We have determined the cross section associated with the plasmonic transition to be in the 1-3x10-13 cm2 range. We have observed that the nanocrystals can be made conductive and photoconductive due to a ligand exchange using a short carboxylic acid, leading to a dark conduction with n-type character. We bring further evidence that the observed photoresponse in the infrared is the result of a bolometric effect

Optoelectronic properties of methyl-terminated germanane

Germanane is a two-dimensional, strongly confined form of germanium. It presents an interesting combination of (i) ease of integration with CMOS technology, (ii) low toxicity, and (iii) electronic confinement which transforms the indirect bandgap of the bulk material into a direct bandgap featuring photoluminescence. However, the optoelectronic properties of this material remain far less investigated than its structural properties. Here, we investigate the photoluminescence and transport properties of arrays of methyl-terminated germanane flakes. The photoluminescence appears to have two contributions, one from the band edge and the other from trap states. The dynamics of the exciton appear to be in the range of 1–100 ns. Conduction in this material appears to be p-type, while the photoconduction time response can be made as short as 100 μs

Nanocristaux colloidaux confinés pour l’optoélectronique infrarouge: dynamique des porteurs et transitions intrabande

Colloidal nanocrystals are crystalline objects grown by colloidal chemistry approaches. Thanks to quantum confinement, their optical properties depend on their size, and can then be tuned accordingly. Using mercury selenide and mercury telluride, we grow infrared-absorbing nanocrystals. While HgTe nanocrystals interband gap can be tuned from the NIR to the MWIR, HgSe nanocrystals display self-doping and intraband transitions in the MWIR to LWIR. With a careful control of their surface chemistry, those nanocrystals can be integrated into electrical devices to create cheap infrared photodetectors. In my PhD work, I am interested in probing carrier dynamics in those devices using various time-resolved techniques, either based on photocurrent measurements or on direct observation of the photocarriers relaxation. From dynamic study of HgSe intraband devices, I identify the issue brought by the degenerative doping level of those nanocrystals: transport is driven by the doping of this material, resulting in very poor IR-sensing performances. By taking inspiration from the III-V semiconductor developments, I propose several successful approaches to uncouple optical and transport properties in HgSe-based, MWIR detectors.Les nanocristaux colloïdaux sont des objets cristallins obtenus par voie chimique. Ces objets étant confinés, leurs propriétés optiques dépendent de leur taille, et peuvent donc être ajustées à la demande. Les nanocristaux de tellurure de mercure et de séléniure de mercure possèdent notamment des propriétés d’absorption dans l’infrarouge: l’énergie de bande interdite (interbande) des nanocristaux de HgTe peut-être variée du SWIR au MWIR, tandis que les nanocristaux de HgSe, grâce à un auto-dopage électronique dégénéré, présentent des transitions intrabande ajustables du MWIR au LWIR. Un contrôle fin de la chimie de surface de ces objets permet de les intégrer dans des dispositifs électroniques et de créer des détecteurs infrarouge à bas coût. Dans mon travail de thèse, je me suis intéressé à différentes manières de sonder la dynamique des porteurs dans ces dispositifs, soit via la mesure du photocourant, soit par des observations directes de la relaxation des porteurs photogénérés. A partir d’études sur la dynamique dans HgSe, j’ai identifié les limitations apportées par le fort dopage de ces nanocristaux : le transportest dominé par la forte densité électronique, conduisant à des faibles performances pour la détection IR. En reprenant les concepts développés pour les hétérostructures de semi-conducteurs III-V, je propose différentes approches fructueuses pour découpler les propriétés optiques et le transport de charges dans des dispositifs de détection MWIR à base de nanocristaux de HgSe

HgTe, the Most Tunable Colloidal Material: from the Strong Confinement Regime to THz Material

International audienceHgTe nanocrystals are extremely interesting materials to obtain a highly tunable absorption spectrum in the infrared range. Here, we discuss the two extreme cases of strongly confined and barely confined HgTe nanocrystals. We discuss the synthesis and optoelectronic properties of HgTe 2D nanoplatelets where the confinement energy can be as large as 1.5 eV. This material presents enhanced (mostly narrower) light emitting properties compared to spherical nanocrystals emitting at the same wavelength. Moreover, absorption spectra, majority carriers and time response can be tuned by carefully choosing the surface chemistry and applying a well-chosen gate bias. HgTe can also be used to explore the effect of vanishing confinement and to obtain quasi bulk properties with tunable absorption in the THz, up to 150 µm

Surface Control of Doping in Self-Doped Nanocrystals

International audienceSelf-doped nanocrystals raise great interest for infrared (IR) optoelectronics because their optical properties span from near to far IR. However, their integration for photodetection requires a fine understanding of the origin of their doping and also a way to control the magnitude of the doping. In this paper, we demonstrate that a fine control of the doping level between 0.1 and 2 electrons per dot is obtained through ligand exchange. The latter affects not only the interparticle coupling but also their optical properties because of the band-shift resulting from the presence of surface dipoles. We demonstrate that self-doping is a bulk process and that surface dipoles can control its magnitude. We additionally propose a model to quantify the dipole involved with each ligand. We eventually use the ligand design rule previously evidenced to build a near-infrared photodetector on a soft and transparent substrate. The latter significantly improves the performance compared to previously reported colloidal quantum dot-based photodetectors on plastic substrates operated in the telecom wavelength range