Patent Application
20250040289
The invention relates to a device used for the detection of infrared light, and in which the active layer consists in particular of HgTe nanocrystals. More precisely, the invention concerns the design of a photodiode absorbing in the range of 1 to 2.5 μm.
Infrared detectors are based on different component geometries. Photoconductors, phototransistors and photodiodes are the most common. The latter geometry is often the one that leads to the highest signal to noise ratio. Typically, photodiodes are based on a vertical stack of layers.
When a photodiode is made from colloidal nanocrystals, a photodiode 1 is generally based on a stack of six layers, as shown in
The vast majority of studies relative to HgTe nanocrystals based photodiode to date have focused on the hole transport layer. For example, Ackerman et al. in ACS Nano 2018, 12, 7264 optimized this layer. They integrated a layer composed of Ag2Te nanocrystals undergoing a chemical process (cation exchange with Hg) as an electron extraction layer. The latter works particularly well when coupled to an absorber layer with a cut-off wavelength above 2.5 μm. The HgTe nanocrystals used with optical properties above 2.5 μm are large size particles (>8 nm) and their majority carriers are electrons. It is therefore essential to focus on the extraction of holes, which are the minority carriers.
The invention is particularly concerned with lower cut-off wavelengths (between 1.7 and 2.5 μm), where the HgTe nanocrystals acquire a p character. This means that the majority carriers are holes (ACS Photonics 2018, 5, 4569). As a result, the ITO/HgTe/Ag2Te/Au stack diode is no longer as efficient in this new wavelength range. Indeed, it is no longer a pn junction but a simple Schottky junction. It is therefore essential to introduce an electron extraction layer in order to make high-performance diodes based on HgTe nanocrystals in this spectral range.
There are two examples in the literature of electron extraction layers that have been coupled to absorbing layers of HgTe nanocrystals.
In Adv. Funct. Mater. 16, 1095 (2006) by Guines et al or in J. Phys Chem C 122, 14979 (2018), by Jagtap et al combines HgTe nanocrystals with a TiO2 layer, the latter being classically used in solar cells. The I-V curve obtained shows a strong rectifying behavior, but the responses are very low (<1 mA.W−1), which makes them very poor detectors. TiO2 is a large band gap n-type oxide. Its band alignment makes hole blocking efficient, which leads to the observed shape of the I-V curves. However, the residual offset between the conduction bands of TiO2 and HgTe makes this layer also filters the generated photoelectrons, which reduces the photoresponse.
In Small 2019, 15, 1804920. Tang et al proposes to use a layer of Bi2Se3 nanoparticles as an electron extraction layer coupled to a layer of absorber nanocrystals in the spectral range of interest. This strategy led to more interesting performances, but the large size of the Bi2Se3 nanoplatelets makes it difficult to obtain a homogeneous layer, i.e. without short-circuiting. In addition, the low band gap of Bi2Se3 leads to inefficient filtration of the dark hole current, which limits the rectifying character of the I-V curve.
The present invention aims to remedy these drawbacks.
The object of the invention is thus an infrared photodetector, comprising an electron transport layer and an infrared photon absorption layer for generating an electrical signal. The presence of the electron transport layer (ETL) allows the charge carrier transport properties to be optimized.
In the photodetector according to the invention, the electron transport layer comprises nanocrystals of a compound selected from SnO2, ZnO, CdS, CdSe, aluminium-doped zinc oxide, Cr2O3, CuO, CuO2, Cu2O3, ZrO2, and mixture thereof, and heterostructure thereof and alloy thereof, and the infrared photon absorption layer comprises nanocrystals of a compound selected from HgS, HgSe, HgTe, PbS, PbSe, PbTe, Ag2S, Ag2Se, Ag2Te, InAs, InGaAs and InSb and mixture thereof and heterostructure thereof and alloy thereof.
Particularly preferably, the infrared photon absorption layer comprises HgTe nanocrystals and the electron transport layer comprises CdSe or SnO2 nanocrystals.
This electron transport layer has a band alignment which is particularly well suited to allow electron extraction from an absorption layer consisting of HgTe.
The introduction of an electron transport layer facilitates the extraction of electrons while reducing the dark current associated with holes. It therefore contributes to the formation of the pn junction in this component, which induces an internal electric field that will participate in charge dissociation, even in the absence of applied voltage. The use of CdSe or SnO2 allows high responses to be obtained thanks to a more favorable band alignment.
The offset between the conduction band of the electron transport layer and the conduction band of the infrared photon absorption layer is preferably less than 1 eV, more preferably less than 0.3 eV and most preferably less than 0.1 eV.
The photodetector may comprise:
The stacking order of the layers may be as described above. In one other embodiment the electron transport layer and the hole transport layer are inverted.
A nanocrystal-based photodiode can thus be obtained on the basis of a stack of layers, in which the absorbing layer is surrounded by a hole transport layer and an electron transport layer which are introduced to selectively promote the extraction of holes and electrons respectively. In addition, two electrodes are added whose role is to extract the photocharge carrier. One of these electrodes is partially transparent in the spectral range of interest to allow light to penetrate the absorbing layer.
The mechanical substrate layer may comprise a compound selected from glass, CaF2, undoped Si, undoped Ge, ZnSe, ZnS, KBr, LiF, Al2O3, KCl, BaF2, CdTe, NaCl, CsBr, MgF2, quartz, CdZnTe, InP, GaAs, thalium bromoiodide, and heterostructure thereof and alloy thereof.
The electronic contact layer may have a thickness of between 1 and 10 μm, and preferably between 10 nm and 3 μm.
The electron transport layer may have a thickness of between 0.5 and 500 nm.
The infrared photon absorption layer may have a thickness of between 1 nm and 3 μm, preferably of between 1 nm and 1 μm.
The infrared photon absorption layer may have an optical gap between 1 and 3 μm, and preferably between 1.5 and 2.5 μm.
The hole transport layer may have a thickness of between 0.5 nm and 500 nm.
The metallic contact layer may have a thickness of between 1 and 10 μm, and preferably of between 10 nm and 3 μm.
The photodetector may be a photodiode.
The infrared photon absorption layer may be coupled to a light resonator.
The invention also relates to an imaging device. The imaging device according to the invention comprises a plurality of photodetectors described above, configured to form an image.
In the imaging device according to claim, the plurality of photodetectors may be coupled to a readout circuit, for example of CMOS technology.
The invention also relates to a camera device. The camera device comprises a plurality of photodetectors described above, configured to form a camera.
In the camera device, the plurality of photodetectors may be coupled to an electronic system, an optical system, and a temperature control system.
Further advantages and features of the present invention will be apparent from the following description, which is given as a non-limiting example with reference to the attached figures:
As illustrated in
The stacking order of the layers may be as described above. In one other embodiment the electron transport layer 4 and the hole transport layer 6 are inverted.
The invention relates in particular to photodiodes in which the layer absorbing the incident photons is made of mercury chalcogenide nanocrystals, in particular HgTe, and whose optical gap is between 1 and 3 μm, and more preferably between 1.5 and 2.5 μm.
Two embodiments are proposed based on CdSe and SnO2 for the electron transport layer. These embodiments allow improved performance. Indeed, the band alignment is specific, i.e. has a large deviation from the valence band of HgTe, while having a conduction band resonant with that of HgTe. The material used is a semiconductor with a band gap larger than that of the HgTe nanocrystals used for absorption.
To avoid forming a mismatch between the conduction bands, it is preferable that CdSe be as unconfined as possible. It is therefore advantageous to grow large CdSe particles (>6 nm) giving a band gap around 650 nm. In addition, to make the layer as conductive as possible, its surface chemistry is advantageously modified by very short ions (S2-) and this layer is annealed at a relatively high temperature (200° C.), to induce sintering of the layer.
The invention allows increased detection performance with a response of 0.8 A.W−1, which corresponds to an external quantum efficiency of 50% and 100% for the internal quantum efficiency. The signal to noise ratio, given by the specific detectivity, reaches 9×1011 Jones at room temperature and 9×1012 Jones at 200 K.
In the targeted spectral range (typically between 1 and 1.7 μm), the dominant technology is based on the InGaAs semiconductor. This is a high-performance technology: low dark current, high quantum efficiency around 80%, very good homogeneity. However, it has certain limitations. Indeed, InGaAs is manufactured by epitaxy on an InP substrate that absorbs light below 900 nm. As a result, InGaAs does not absorb visible light, which means that a complementary camera is needed to image the visible part of the spectrum. Attempts have been made to refine the substrate a posteriori, but this remains in the research stage. Epitaxy also dictates the cut-off wavelength of the material (1.8 μm at room temperature and 1.65 μm when cold). Indeed, the composition of the InGaAs alloy is optimized so that the lattice parameter of InGaAs is the same as that of the InP substrate. It is therefore difficult to extend the spectral range of InGaAs. In contrast, the nanocrystals used in the photodetector according to the invention do not have this epitaxial constraint and it is therefore very easy to adjust their cut-off wavelength in the 1-5 μm range.
Another limitation of InGaAs is its cost. The cost of InGaAs is due to the epitaxial growth and the hybridization coupling step using small indium beads between the III-V semiconductor and the readout circuit. The yield of this process is low, which increases the cost. A second limitation of this hybridization step is that it makes difficult to reduce the pixel pitch. In a camera, the pixel size should ideally be very close to the diffraction limit (i.e. pixel size=cut-off wavelength). Currently for InGaAs, the pixel pitch is around 15 μm or 10 times the cut-off wavelength. Major research efforts are trying to reduce the pixel pitch to 10 μm (or even 5 μm). The use of nanocrystals makes it possible to avoid this hybridization step.
The photodetector may have a detection wavelength that is centered on a value between about 800 nm and about 5 μm, more preferably between about 1000 nm and 3 μm, even more preferably between about 1400 nm and 2.5 μm.
The photodetector may provide two-color detection and one of the wavelengths is centered at a value between about 800 nm and about 5 μm, more preferably between about 1 μm and 3 μm, still more preferably between about 1.4 μm and 2.5 μm.
The photodetector may allow for multi-colour detection.
The photodetector may have a temporal response ranging from about 1 ps to about 1 ms, more preferably from about 1 ns to about 100 ps, even more preferably from about 10 ns to about 3 ps.
The photodetector may have a response ranging from about 1 mA.W−1 to about 2 A.W−1, more preferably from about 10 mA.W−1 to about 2 A.W−1, even more preferably from about 0.1 A.W−1 to about 2 A.W−1.
The photodetector may have a detectivity between about 106 and about 1014 Jones, more preferably between about 108 and about 1013 Jones.
The photodetector may have a bandwidth from about 1 Hz to about 1 GHz, more preferably from about 10 Hz to about 100 MHz.
The photodetector may operate at a temperature ranging from about 4 K to about 350 K, preferably from about 50 K to about 310 K, more preferably from about 70 K to about 300 K.
The photodetector may be illuminated from the front or the back side.
The substrate
The substrate may be electrically insulating.
The resistivity of the substrate may be greater than about 100Ω.cm.
The substrate may be partially or fully optically transparent in the infrared range.
The substrate may be partially or fully optically transparent from about 800 nm to about 5 μm, more preferably from about 1 μm to 3 μm, even more preferably from about 1 μm to 2.5 μm.
The substrate may have an optical transmission ranging from about 0% to about 100%, more preferably from about 50% to about 100%, still more preferably from about 80% to 100%.
The substrate may comprise, but is not limited to, glass, CaF2, undoped Si, undoped Ge, ZnSe, ZnS, KBr, LiF, Al2O3, KCl, BaF2, CdTe, NaCl, CsBr, GaAs, MgF2, CdZnTe, InP, GaAs, quartz, KRS-5 (thalium bromoiodide), a stack thereof, or a mixture thereof or a heterostructure thereof.
Each electronic contact layer may be a metallic contact.
The electronic contact layers may have a thickness of between about 1 nm and about 200 nm, more preferably between about 5 nm and 100 nm.
One of the electronic contact layers may be partially or fully optically transparent in the infrared range.
One of the electronic contact layers may be partially or fully optically transparent from about 800 nm to about 5 μm, more preferably from about 1 μm to 3 μm, even more preferably from about 1.4 μm to 2.5 μm.
The electronic contact layers may include, but are not limited to, Au, Ag, Al, Ni, W, Ti, Cr, Pt, Cu, ITO or FTO.
One of the electron contact layers may be used as an electron extractor and the other may be used as a hole extractor.
The electron contact layers may have a work function of from about 6 eV to about 3 eV, more preferably from about 5.5 eV to 4 eV.
The electron contact layers may be obtained by thermal evaporation, sputtering or optical lithography.
The electron transport layer is advantageously made of a material whose conduction band has a small offset with the conduction band of the HgTe nanocrystals having a band gap energy between 1.4 and 2.5 μm. The offset between the conduction band of the electron transport layer and the absorbing layer is typically less than 1 eV, preferably less than 0.3 eV and more preferably less than 0.1 eV.
The electron transport layer may be used to extract electrons from the photoactive layer.
The electron transport layer may have a work function between about 5.5 eV and about 3 eV, more preferably between about 5 eV and 3.5 eV.
The electron transport layer may have an optical transmission ranging from about 0% to about 100%, more preferably from about 50% to about 100%, even more preferably from about 80% to 100%.
The electron transport layer may have an electron mobility ranging from about 10−4 cm2.V−1.s−1 to about 50 cm2.V−1.s−1, more preferably from about 0.01 cm2.V−1.s−1 to about 5 cm2.V−1.s−1.
The electron transport layer may have a real optical index between about 1 and about 4, more preferably between about 1.4 and about 2.5.
The electron transport layer may have a thickness ranging from about 0.5 nm to about 500 nm, more preferably from about 5 nm to about 250 nm, even more preferably from about 10 nm to about 100 nm.
The nanocrystals of the electron extraction layer may have a size ranging from about 0.5 nm to about 100 nm, more preferably from about 1 nm to about 50 nm, even more preferably from about 2 nm to about 20 nm.
The electron transport layer may be obtained by drop-casting, spin-coating, spray-coating, ink-jet, nanoimprinting, dip-coating, doctoring, Langmuir-Blodgett method, electrophoretic procedure, thermal evaporation, or sputtering.
The electron transport layer may comprise, but is not limited to, SnO2, ZnO, CdS, CdSe, AZO (aluminium-doped zinc oxide), Cr2O3, CuO, CuO2, Cu2O3, ZrO2, and mixture thereof, and heterostructure thereof and alloy thereof.
The electron transport layer may not consist of Bi2Se3.
The photoactive layer may be a photoabsorbent film of semiconductor nanoparticles.
The photoactive layer may be obtained by deposition of nanocrystals by drop-casting, spin-coating, spray-coating, ink-jet, nanoimprinting, dip-coating, scraping, Langmuir-Blodgett method or electrophoretic procedure.
The photoactive layer may consist of nanoparticles having infrared absorption.
The physical mechanism responsible for the infrared absorption may be an interband or intraband transition.
The semiconductor nanoparticles may have a band gap of about 0.25 eV to about 1.55 eV, more preferably about 0.41 eV to about 1.24 eV, even more preferably about 0.5 V to about 0.89 eV.
The photoabsorbent layer may have a real optical index between about 1 and about 4, more preferably between about 1.7 and about 2.8.
The size of the nanoparticles may be between about 1 nm and about 1 μm. With respect to the shape of the particles, the particles may be spheres, nanoplatelets, rods, tripods, or tetrahedra.
The nanoparticles can be a p-type semiconductor, an ambipolar semiconductor or an n-type semiconductor.
The doping of the nanocrystals may be from about 0 to about 1000 electrons per nanocrystal, more preferably from about 10−10 to about 100 electrons per nanocrystal, even more preferably from about 10−6 to about 1 electron per nanocrystal.
The doping level may be in particular between about 1015 cm−3 and about 1021 cm−3, more preferably between about 1017 cm−3 and about 1020 cm−3, even more preferably between about 1018 cm−3 and about 1020 cm−3.
The photoabsorbent layer may have a hole mobility between about 10−4 cm2.V−1.s−1 and about 50 cm2.V−1.s−1, more preferably between about 10−2 cm2.V−1.s−1 and about 10 cm2.V−1.s−1.
The photoabsorbent layer may have an electron mobility between about 10−4 cm2.V−1.s−1 and about 50 cm2.V−1.s−1, more preferably between about 10−2 cm2.V−1.s−1 and about 10 cm2.V−1.s−1.
The photoabsorbent layer may have a thickness between about 10 nm and about 1 μm, more preferably between about 100 nm and about 600 nm.
The photoactive layer may be a multilayer structure.
The photoactive layer may be a multilayer structure comprising a layer of p-type material and an ambipolar layer.
The photoactive layer may comprise, but is not limited to, HgS, HgSe, HgTe, PbS, PbSe, PbTe, Ag2S, Ag2Se, Ag2Te, InAs, InGaAs or InSb and alloy thereof, and mixture thereof, and heterostructure thereof.
The hole transport layer may be made of a material whose conduction band has a low offset with the conduction band of HgTe nanocrystals having a band gap energy between 1.5 and 2.5 μm. The offset between the conduction band of the hole transport layer and the absorber layer is typically less than 1 eV, preferably less than 0.3 eV and more preferably less than 0.1 eV.
The hole transport layer may be used to extract holes from the photoactive layer.
The hole transport layer may have a work function between about 7 eV and about 3.5 eV, more preferably between about 6 eV and 4 eV.
The hole transport layer may have a hole mobility between about 10−4 cm2.V−1.s−1 and about 50 cm2.V−1.s−1, more preferably between about 0.01 cm2.V−1.s−1 and about 10 cm2.V−1.s−1.
The hole transport layer may have a thickness ranging from about 0.5 nm to about 500 nm, more preferably from about 5 nm to about 250 nm, even more preferably from about 10 nm to about 100 nm.
The hole transport layer may be obtained by drop casting, spin coating, spray coating, ink jet, nano printing, dip coating, doctoring, Langmuir-Blodgett method, electrophoretic procedure, thermal evaporation or spraying.
The hole transport layer may consist of an inorganic material.
The hole transport layer may include, but is not limited to, Ag2Te, HgTe, PbS, MoO3, CuSCN, V2O5, WO3, NiO, CrOx, ReO3, RuOx, Cu2O, CuO, where x is a decimal ranging from 0 to 5, and alloy thereof, and mixture thereof, and heterostructure thereof.
The hole transport layer may consist of nanoparticles.
The hole transport layer may consist of a conductive polymer.
The hole transport layer may consist of a p-type conductive polymer.
The hole transport layer may consist of a conductive polymer such as P3HT or PEDOT:PSS.
The nanoparticles of the hole transport layer may have a size ranging from about 0.5 nm to about 100 nm, more preferably from about 1 nm to about 50 nm, even more preferably from about 2 nm to about 20 nm.
The photodetector may comprise a single pixel.
The photodetector may comprise a plurality of pixels.
The pixels may form a pixel line.
The pixels may form a pixel array.
The size of the pixel array may be between about 4×4 pixels and about 16384×12288 pixels, more preferably between about 320×200 pixels and about 16384×12288 pixels.
The array may have a number of pixels ranging from about 16 to about 300 M pixels, more preferably from about 1000 to about 202 M pixels.
The area of the pixels may be from about 1 nm2 to about 1 mm2, more preferably from about 100 nm2 to about 0.1 mm2.
The pitch of the pixels may be between about 0.1 μm and about 10 mm, more preferably between about 1 μm and about 1 cm.
The pixels may be non-overlapping.
Each pixel may be coupled to a readout circuit.
Each pixel may be coupled to a readout circuit in a vertical geometry.
The pixel array may be coupled to a readout circuit.
The pixel array may be coupled to a vertical geometry.
Each pixel can be coupled to a CMOS readout circuit (for «Complementary Metal Oxide Semiconductor»).
The pixel array can be coupled to a CMOS readout circuit.
Each pixel may be operated under electric field which absolute value ranges from 0 to 100 kV.cm−1.
Each pixel may be operated under bias which absolute value ranges from 0 to 10 V and preferably from 0 to 3 V.
Each pixel may be operated at 0 V in photovoltaic mode.
The pixel array can be operated at 0 V in photovoltaic mode.
The photodetector can be included in an infrared camera.
The photodetector is coupled to a light resonator.
The light resonator coupled to the absorbing layer is a Fabry-Perot cavity, a grating, a guided mode resonator, a plasmonic cavity
As shown in
The I-V (current-voltage) curve in the dark is well asymmetrical and the conduction minimum of the curve under illumination is shifted.
In another embodiment of the invention, illustrated in
An attempt was made to characterize the performance of the photodiode.
It was determined that the photoresponse of these components reaches 0.8 A.W−1 which corresponds to an external quantum efficiency (number of electrons generated per incident photon) of 50%. Furthermore, the absorption of this device was simulated and it was determined that the active layer absorbs 50% of the incident light.
This means that the internal quantum efficiency of this diode is close to 100% (
The performance of this diode was determined by characterizing the specific detectivity (which quantifies the signal to noise ratio). The performance is above the state of the art for a HgTe based photodiode. The specific detectivity is 9×1010 Jones at room temperature and 9×1011 Jones at 200 K (
Moreover, the response time of this device is short (<1 ps) and can even go down to around 200 ns for small devices (
The present invention is further illustrated by the following examples.
1 M TOP:Te Precursor
2.54 g of Te powder was mixed with 20 mL of TOP (trioctylphosphine) in a three neck flask. The flask was kept under vacuum at room temperature for 5 min and then the temperature was increased to 100° C. In addition, the flask was degassed for the next 20 min. The atmosphere was replaced with nitrogen and the temperature was raised to 275° C. The solution was stirred until a light orange color was obtained. The flask was cooled to room temperature and the color changed to yellow. Finally, this solution was transferred to a nitrogen-filled glove box for storage.
0.1 M Se-ODE precursor
In a 100 mL three neck flask, 46.7 mL of ODE (octadecene) were degassed at room temperature for 30 minutes. During this time, a suspension of 393 mg Se in 3 mL ODE was prepared. After degassing, the atmosphere was changed to nitrogen and the temperature was raised to 170° C. The suspension was added in portions (300 μL), waiting between each addition for complete dissolution of the Se. Once all the Se was completely dissolved in the ODE, the solution was heated for 1 h at 215° C.
The solution turned reddish-orange to yellow. The flask was cooled to room temperature. The solution was transferred to a glove box.
In a 100 mL three neck flask, 2.56 g CdO and 11 g myristic acid were degassed under vacuum for 30 minutes at 70° C. Under an argon flow, the mixture was heated at 200° C. for 30 minutes until the solution became colorless. Then 50 mL of MeOH was added at 60° C. to 70° C. to solubilize the excess myristic acid. The mixture was stirred for 30 minutes. At the end, the cadmium myristate was precipitated using a centrifuge tube by adding MeOH. The washing procedure was repeated at least three times. The cadmium myristate was dried overnight under vacuum.
0.5 M cadmium oleate solution was synthesized by heating 10 mmol of cadmium oxide in 20 mL of oleic acid at 160° C. under Ar until a colorless solution was obtained. The solution was then degassed under vacuum at 100° C. for 1 h.
In a 50 mL three neck flask, 540 mg of HgCl2 and 50 mL of oleylamine were degassed under vacuum at 110° C. At this stage, the solution was yellow and clear. Meanwhile, 2 mL of TOP:Te (1M) was extracted from the glove box and was mixed with 8 mL of oleylamine. The atmosphere was switched to N2 and the temperature was set at 57° C. The pre-heated TOP:Te solution was quickly injected and the solution turned dark after 1 min. After 3 min, 10 mL of a mixture of 10% DDT (dodecanethiol) in toluene was injected and a water bath was used to quickly decrease the temperature. The content of the flask has been split in 4 tubes and methanol was added. After centrifugation, the formed pellets were redispersed in one tube with 10 mL of toluene. The solution was precipitated a second time with absolute ethanol.
Again, the formed pellet was redispersed in 8 mL of toluene. At this step, the nanocrystals were centrifuged in pure toluene to remove the lamellar phase. The solid phase was discarded and the supernatant filtrated.
In a 50 mL three neck flask, 540 mg of HgCl2 and 50 mL of oleylamine were degassed under vacuum at 110° C. At this stage, the solution was yellow and clear. Meanwhile, 2 mL of TOP:Te (1M) was extracted from the glove box and was mixed with 8 mL of oleylamine. The atmosphere was switched to N2 and the temperature was set at 86° C. The pre-heated TOP:Te solution was quickly injected and the solution turned dark after 1 min. After 3 min, 10 mL of a mixture of 10% DDT in toluene was injected and a water bath was used to quickly decrease the temperature. The content of the flask has been split in 4 tubes and methanol was added. After centrifugation, the formed pellets were redispersed in one tube with 10 mL of toluene. The solution was precipitated a second time with absolute ethanol. Again, the formed pellet was redispersed in 8 mL of toluene. At this step, the nanocrytsals were centrifuged in pure toluene to remove the lamellar phase. The solid phase was discarded and the supernatant filtrated.
In a 25 ml three neck flask, 34 mg AgNO3 (0.2 mM), 5 mL oleylamine and 0.5 mL oleic acid were degassed at 70° C. under vacuum until the AgNO3 was completely dissolved and the solution became clear. Under nitrogen, 0.5 mL TOP was injected into the solution. Then temperature was raised to 160° C. At 160° C. the solution became orange. Now 0.1 mL TOPTe (1 M) was injected into the solution and the reaction was quenched after 10 min with a water bath. The nanocrystals were precipitated with methanol and redispersed in chlorobenzene. At this step, 500 μL of dodecanethiol were added. The washing step was repeated one more time and finally the nanocrystals were redispersed in hexane:octane (9:1) solution.
In a 100 mL three neck flask, 170 mg of cadmium myristate and 7.5 mL of octadecene were degassed at room temperature for 30 min. Then, the reaction was put under nitrogen and heated up at 250° C. Meanwhile, a suspension of Se (24 mg) in 2 mL of octadecene was prepared. At 250° C., 1 mL of this solution was rapidly injected (suspension is sonicated just before the injection). Immediately after the injection, the temperature controller was set at 240° C. and the reaction is heated for 5 min. After this time, 200 μL of oleic acid have been added and the temperature controller was set at 260° C. At 260° C., 2 m L of oleylamine were added and the reaction was heated for 10 min. Meanwhile, 2 mL of cadmium oleate 0.5 M and 10 mL of Se-octadecene 0.1 M were mixed. 11 mL of the previous mixture was injected with a flow rate of 10 mL/h. Then, the reaction was left cooling down to room temperature. The reaction mixture has been split into two tubes and the round-bottomed flask was rinsed with 10 mL of Hexane which were distributed in two tubes. The particles were precipitated by adding 30 mL of ethanol in each tube. The mixtures were centrifuged at 6000 rpm for 10 min. The supernatants were discarded and both pellets (containing mainly the CdSe cores) were assembled into 10 mL of hexane. The CdSe nanocrystals were precipitated with 40 mL of ethanol. The mixture was centrifuged at 5500 rpm for 10 min. The supernatant was discarded and the pellet was dispersed into 10 mL of hexane.
1 mL of HgTe CQDs solution in toluene was mixed with 1 mL of exchange solution (1.5 mg of HgCl2, 100 μL of mercaptoethanol and 900 μL of DMF). 5 mL of hexane was added to the solution and mixed with vortex and sonication. After a few seconds, two phases were clearly visible and the hexane one was removed. The solution was cleaned with hexane one more time. At this step, 250 μL of DMF was added to avoid precipitation. The solution was cleaned again with hexane. Then, the solution was precipitated by adding ethanol and centrifuged at 6000 rpm for 4 min. Supernatant was discarded and the nanocrystals were redispersed in 150 μL of DMF.
440 μL of CdSe nanocrystals solution in hexane (exciton optical density=0.58 after a dilution by 100) with optical properties at 640 nm were mixed with 800 μL of Na2S solution (0.1 M in N). After mixing, 2 mL of hexane were added. The top phase was removed. The solution was washed with hexane two more times. The solution was precipitated by adding toluene (5 mL) and centrifuged at 6000 rpm for 2 min. The supernatant was discarded and the nanocrystals were redispersed in 100 μL of DMF. 5 mL of toluene were added and the nanoparticles were precipitated at 6000 rpm for 2 min. The supernatant was discarded and the nanocrystals were redispersed in 100 μL of DMF.
400 μL of SnO2 nanoparticle solution (15% in water) marketed by the company Alfa Aeser was diluted with 0.8 mL of distilled water.
400 μL of SnO2 nanoparticle solution (15% in water) marketed by Alfa Aeser was mixed with 0.8 mL of 24 mM NH4Cl solution in distilled water.
200 μL of SnO2 nanoparticle solution (15% in water) marketed by Alfa Aeser was mixed with 1 mL of 24 mM NH4X (X=Cl, Br and I) solution in distilled water.
200 μL of SnO2 nanoparticle solution (15% in water) marketed by Alfa Aeser was mixed with 1 mL of NH4X (X=Cl, Br and I) solution at 48 mM in distilled water.
The electrodes were fabricated using standard optical lithography methods. The surface of an FTO substrate (70 nm thick) on glass was cleaned by ultrasonication in acetone. The substrate was rinsed with isopropanol and finally cleaned using 02 plasma. The adhesion promoter (Ti-prime) was deposited by spin coating and baked at 120° C. for 180 s. The resist marketed as AZ®5214E by Merck was spin-coated and cured at 110° C. for 90 s. The substrate was exposed to UV light through a patterned mask for 20 s. The resist was developed using a bath marketed as AZ®726 by Merck for 30 s, before being rinsed with pure water. The FTO was then etched using reactive ion etching. The patterning was achieved by soaking the film for 15 min in acetone. The electrodes were then rinsed with isopropanol and dried by nitrogen flow.
Electrodes were fabricated using standard optical lithography methods. The surface of a ITO (40 nm thick) on glass substrate was cleaned by sonication in acetone.
The substrate was rinsed with isopropanol and finally cleaned using a 02 plasma. Ti prime was deposited via spin coating and baked at 120° C. for 180 s. The resist marketed under the name AZ®5214E by Merck was spin-coated and baked at 110° C. for 90 s. The substrate was exposed under UV through a pattern mask for 20 s. The resist was developed using a bath marketed under the name AZ®726 by Merck for 30 s, before being rinsed with pure water. The ITO was etched with HCl bath (25%) at 40° C. for 2 min. The lift-off is performed by dipping the film for 15 min in acetone. The electrodes were finally rinsed using isopropanol and dried by nitrogen flow.
The FTO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to ozone plasma for 10 min. The CdSe ink was deposited onto the patterned FTO substrate via spin coating (800 rpm for 2 min). The CdSe film was annealed on a hot plate at 200° C. for 20 min. The HgTe nanocrystals ink was deposited onto the CdSe film via spin coating at room temperature. The thickness of the film was tuned with spin coating speed and ink concentration in DMF solvent. On top of HgTe ink film, a Ag2Te nanocrystals layer was spin coated at 2000 rpm followed by HgCl2 treatment. For HgCl2 treatment, 50 μL of HgCl2 methanol (10 mM) solution was dropped onto HgTe film and spin-dried after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated one more time. Finally, an ethanedithiol ligand-exchange was performed by dipping the film in 1% ethanedithiol in acetonitrile solution for 30 s and rinsed with pure acetonitrile. An 80 nm Au top electrode was deposited with thermal evaporation under a vacuum of ≈5×10−6 mbar at the rate of 3 A/s. The thickness was monitored with in situ quartz crystals. The substrate holder was rotated during the deposition to ensure homogeneous thickness.
The ITO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to ozone plasma for 10 min. The CdSe ink was deposited onto the patterned ITO substrate via spin coating (800 rpm for 2 min). The CdSe film was annealed on a hot plate at 200° C. for 20 min. The HgTe nanocrystals ink was deposited onto the CdSe film via spin coating. The thickness of the film was tuned with spin-coating speed and ink concentration in DMF solvent. On top of HgTe ink film, Ag2Te nanocrystals layer was spin-coated at 2000 rpm followed by HgCl2 treatment. For HgCl2 treatment, 50 μL of HgCl2 methanol (10 mM) solution was dropped onto HgTe film and spin-dried after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated one more time. Finally, an ethanedithiol ligand-exchange was performed by dipping the film in 1% ethanedithiol in acetonitrile solution for 30 s and rinsed with pure acetonitrile. An 80 nm Au top electrode was deposited with thermal evaporation under a vacuum of =5×10−6 mbar at the rate of 3 A/s. The thickness was monitored with in situ quartz crystals. The substrate holder was rotated during the deposition to ensure homogeneous thickness.
The FTO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to ozone plasma for 10 min. The SnO2-L″ solution was deposited onto the patterned FTO substrate via spin-coating. The SnO2-H solution was deposited onto the SnO2-L layer. The film was annealed on a hot plate at 70° C. The HgTe nanocrystals ink was deposited onto the SnO2 film via spin coating. The thickness of the film was tuned with spin coating speed and ink concentration in DMF solvent. On top of HgTe ink film, Ag2Te nanocrystals layer was spin-coated at 2000 rpm followed by HgCl2 treatment. For HgCl2 treatment, 50 μL of HgCl2 methanol (10 mM) solution was dropped onto HgTe film and spin-dried after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated one more time. Finally, an ethanedithiol ligand-exchange was performed by dipping the film in 1% ethanedithiol in acetonitrile solution for 30 s and rinsed with pure acetonitrile. An 80 nm Au top electrode was deposited with thermal evaporation under a vacuum of =5×10−6 mbar at the rate of 3 A/s. The thickness was monitored with in situ quartz crystals. The substrate holder was rotated during the deposition to ensure homogeneous thickness.
The ITO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to ozone plasma for 10 min. The SnO2-L″ solution was deposited onto the patterned ITO substrate via spin-coating. The SnO2-H solution was deposited onto the SnO2-L layer. The film was annealed on a hot plate at 70° C. The HgTe nanocrystals ink was deposited onto the SnO2 film via spin-coating. The thickness of the film was tuned with spin-coating speed and ink concentration in DMF solvent. On top of HgTe ink film, Ag2Te nanocrystals layer was spin-coated at 2000 rpm followed by HgCl2 treatment. For HgCl2 treatment, 50 μL of HgCl2 methanol (10 mM) solution was dropped onto HgTe film and spin-dried after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated one more time. Finally, an ethanedithiol ligand-exchange was performed by dipping the film in 1% ethanedithiol in acetonitrile solution for 30 s and rinsed with pure acetonitrile. An 80 nm Au top electrode was deposited with thermal evaporation under a vacuum of =5×10−6 mbar at the rate of 3 A/s. The thickness was monitored with in situ quartz crystals. The substrate holder was rotated during the deposition to ensure homogeneous thickness.
The FTO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to ozone plasma for 10 min. The SnO2-P solution was deposited onto the patterned FTO substrate via spin-coating. The SnO2-L′ solution is deposited onto the SnO2-L layer. The film was annealed on a hot plate at 70° C. The HgTe nanocrystals ink was deposited onto the SnO2 film via spin-coating. The thickness of the film was tuned with spin-coating speed and ink concentration in DMF solvent. On top of HgTe ink film, Ag2Te nanocrystals layer was spin-coated at 2000 rpm followed by HgCl2 treatment. For HgCl2 treatment, 50 μL of HgCl2 methanol (10 mM) solution was dropped onto HgTe film and spin-dried after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated one more time. Finally, an ethanedithiol ligand-exchange was performed by dipping the film in 1% ethanedithiol in acetonitrile solution for 30 s and rinsed with pure acetonitrile. An 80 nm Au top electrode was deposited with thermal evaporation under a vacuum of =5×10−6 mbar at the rate of 3 A/s. The thickness was monitored with in situ quartz crystals. The substrate holder was rotated during the deposition to ensure homogeneous thickness.
The FTO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to an ozone plasma for 10 minutes. The CdSe ink was deposited onto the patterned FTO substrate by centrifugation (800 rpm for 2 min). The CdSe film was annealed on a hot plate at 200° C. for 20 min. 80 μL of concentrated HgTe nanocrystals (25 mg/mL) from toluene were deposited by centrifugation at 2000 rpm for 30 s on the CdSe film. After complete evaporation of the solvent, ligand exchange is performed by dipping the film in a 1-2 wt % ethanedithiol solution in ethanol for 90 s and rinsing in pure ethanol for 30 s. This procedure is repeated 8-9 times to obtain a thicker HgTe film (180-200 nm) without holes. On the HgTe film, a layer of Ag2Te nanocrystals was deposited by centrifugation at 2000 rpm followed by HgCl2 treatment. For the HgCl2 treatment, 50 μL of HgCl2-methanol (10 mM) solution was deposited on the HgTe film and spun off after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated once more. Finally, an ethanedithiol ligand exchange was performed by dipping the film in a solution of ethanedithiol in 1% acetonitrile for 30 s and rinsing with pure acetonitrile. An 80 nm Au top electrode was deposited by thermal evaporation under a vacuum of ≈5×10−6 mbar at the rate of 3 A/s. The thickness was controlled with quartz crystals in situ. The substrate holder was rotated during deposition to ensure a homogeneous thickness.
The FTO-coated glass substrates were sequentially cleaned in acetone and isopropanol. The substrates were exposed to an ozone plasma for 10 minutes. The SnO2-L solution was deposited onto the patterned FTO substrate by spin coating. The SnO2-L″ solution was deposited on the SnO2-L layer. The film was annealed on a hot plate at 70° C. 80 μL of concentrated HgTe nanocrystals (25 mg/mL) from toluene were deposited by spin coating at 2000 rpm for 30 s on the above SnO2 layer. After complete evaporation of the solvent, ligand exchange is performed by dipping the film in a 1-2 wt % ethanedithiol solution in ethanol for 90 s and rinsing in pure ethanol for 30 s. This procedure is repeated 8-9 times to obtain a thicker HgTe film (180-200 nm) without holes. On the HgTe film, a layer of Ag2Te nanocrystals was deposited by centrifugation at 2000 rpm followed by HgCl2 treatment. For the HgCl2 treatment, 50 μL of HgCl2-methanol (10 mM) solution was deposited on the HgTe film and spun off after 15 s. Then the film was rinsed with isopropanol. This procedure was repeated once more. Finally, an ethanedithiol ligand exchange was performed by dipping the film in a 1% ethanedithiol in acetonitrile solution for 30 s and rinsing with pure acetonitrile. An 80 nm Au top electrode was deposited by thermal evaporation under a vacuum of ≈5×10−6 mbar at the rate of 3 A/s. The thickness was controlled with quartz crystals in situ. The substrate holder was rotated during deposition to ensure a homogeneous thickness.
A CMOS technology readout circuit is cleaned by oxygen plasma for 10 min. A layer of Ag2Te nanocrystals was deposited by centrifugation at 2000 rpm, followed by HgCl2 treatment. For the HgCl2 treatment, 50 μL of HgCl2 methanol solution (10 mM) was deposited on the HgTe film and blotted after 15 s. Then the film was rinsed with isopropanol. The HgTe nanocrystals ink was deposited on the Ag2Te nanocrystal film by spin coating. The thickness of the film was adjusted according to the application speed and the concentration of the ink in the DMF solvent. On the HgTe nanocrystal layer, the SnO2-H solution was deposited by spin coating. On the SnO2-H nanocrystal layer, the SnO2-L solution was deposited by spin coating. Using plasma assisted deposition, a thin layer of ITO was deposited to form a continuous layer of 50 nm.
A CMOS technology readout circuit is terminated with Au top contact and cleaned by oxygen plasma for 10 min. On the CMOS circuit, a SnO2 solution was deposited by spin coating. The HgTe nanocrystals ink was deposited on the SnO2 nanocrystal film by spin coating. A layer of Ag2Te nanocrystals was deposited by centrifugation at 2000 rpm, followed by HgCl2 treatment. For the HgCl2 treatment, 50 μL of HgCl2 methanol solution (10 mM) was deposited on the HgTe film and blotted after 15 s. Then the film was rinsed with isopropanol. Using sputtering deposition, a thin layer of ITO was deposited to form a continuous layer of 50 nm.
A CMOS technology readout circuit is terminated with Al top contact and cleaned by oxygen plasma for 10 min. On the CMOS circuit, a SnO2 solution was deposited by spin coating. The HgTe nanocrystals ink was deposited on the SnO2 nanocrystal film by spin coating. A layer of Ag2Te nanocrystals was deposited by centrifugation at 2000 rpm, followed by HgCl2 treatment. For the HgCl2 treatment, 50 μL of HgCl2 methanol solution (10 mM) was deposited on the HgTe film and blotted after 15 s. Then the film was rinsed with isopropanol. Using sputtering deposition, a thin layer of ITO was deposited to form a continuous layer of 50 nm.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2021/000954 | 12/8/2021 | WO |
