CN112086531B - Molecular material component applied to high-sensitivity photoelectric detector and manufacturing method thereof - Google Patents
Molecular material component applied to high-sensitivity photoelectric detector and manufacturing method thereof Download PDFInfo
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- CN112086531B CN112086531B CN202010929848.8A CN202010929848A CN112086531B CN 112086531 B CN112086531 B CN 112086531B CN 202010929848 A CN202010929848 A CN 202010929848A CN 112086531 B CN112086531 B CN 112086531B
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- Light Receiving Elements (AREA)
Abstract
The embodiment of the application discloses a molecular material part applied to a high-sensitivity photoelectric detector and a manufacturing method thereof, wherein the molecular material part is a PN junction applied to the high-sensitivity photoelectric detector, the molecular material comprises colloid quantum dots, and the method comprises the following steps: manufacturing a colloid quantum dot film according to a preset mode, wherein the colloid quantum dot film is used as a P-type surface incidence window layer of the PN junction; manufacturing an N-type intrinsic absorption layer, and spin-coating the N-type intrinsic absorption layer by using metal oxide to obtain the N-type intrinsic absorption layer modified by the metal oxide; and arranging the colloid quantum dot film on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide by adopting a photoetching process to obtain a PN junction. By adopting the method and the device, the PN junction formed by the P-type surface incident window layer and the semiconductor channel layer manufactured by the colloid quantum dot film can generate a built-in electric field, so that the service life of a photon-generated carrier is prolonged, and the photoelectric effect is enhanced.
Description
Technical Field
The application relates to the technical field of photoelectric detection, in particular to a molecular material component applied to a high-sensitivity photoelectric detector and a manufacturing method thereof.
Background
With the development of the photoelectric detection technology, substances applied to the technical field of photoelectric detection are more and more extensive. Optical sensors operating in the mid to long wavelength infrared bands have many applications including gas detection, thermal imaging, and the detection of environmental hazards. Since the mechanical stripping of graphene was successful in 2004, the exploration and research development of low-dimensional semiconductor materials are fast inspired by ultrathin two-dimensional nanomaterials. The zero-dimensional material is typically represented by Quantum Dots (QDs). QDs, also known as semiconductor Nanocrystals (NCs), refers to three-dimensionally confined nanomaterials with radii smaller than or close to the exciton bohr radius. In the field of photoelectric application, Colloid Quantum Dots (CQDs) have obvious quantum confinement effect, can provide a process platform for liquid phase processing devices, is the basis for constructing low-power-consumption and high-performance photoelectric detectors, and is a new candidate material for developing new-generation high-performance electronic devices.
However, since CQDs rely on interband absorption of light, there is a high demand for the energy of the incident photons to achieve electron excitation. And many QDs technologies are concerned with the fact that lead and mercury are not only toxic, but also subject to international regulations on the restriction of hazardous substances, and also cause environmental pollution. How to improve the production process of CQDs, make it exert its advantage when applying to the photodetector, at the same time, overcome its deficiency.
Disclosure of Invention
The embodiment of the application provides a molecular material component applied to a high-sensitivity photoelectric detector and a manufacturing method thereof. The sensitivity of the molecular material component is improved by improving the substances and modes for manufacturing the molecular material.
In a first aspect, a method for manufacturing a molecular material component applied to a high-sensitivity photodetector, the molecular material component being a PN junction applied to the high-sensitivity photodetector, the molecular material including colloidal quantum dots, the method includes:
manufacturing a colloid quantum dot film according to a preset mode, wherein the colloid quantum dot film is used as a P-type surface incidence window layer of the PN junction;
manufacturing an N-type intrinsic absorption layer, and spin-coating the N-type intrinsic absorption layer by using metal oxide to obtain the N-type intrinsic absorption layer modified by the metal oxide, wherein the N-type intrinsic absorption layer comprises a semiconductor material;
and arranging the colloid quantum dot film on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide by adopting a photoetching process to obtain a PN junction.
Optionally, the manufacturing of the colloidal quantum dot film according to a preset method includes:
preparing a reaction solvent according to a certain proportion, heating the reaction solvent to 300-500 ℃, and injecting an organic precursor into the reaction solvent;
decomposing the organic precursor by adopting a high-energy decomposition mode, so that the organic precursor is gasified to generate an active intermediate, wherein the high-energy decomposition mode comprises any one or more of heating decomposition, laser decomposition and plasma reaction decomposition;
adjusting the temperature in the reactor so that the active intermediate vapor temperature is higher than the thermodynamic critical reaction temperature value, and forming saturated vapor pressure in the reactor so that the active intermediate spontaneously condenses and nucleates;
controlling the temperature within the reactor such that the nuclei aggregate to form microparticles in a heating zone of the reactor and nanocrystals are formed at a temperature;
inputting carrier gas flow into the reactor, so that the carrier gas flow transports the nanocrystalline to a low-temperature region of the reactor, and colloidal quantum dots are formed through grain growth and aggregation;
and manufacturing the colloidal quantum dots into the colloidal quantum dot film according to a preset process.
Optionally, the manufacturing the colloidal quantum dot film by using the colloidal quantum dot according to a preset process includes:
detecting the size of the colloidal quantum dots, and centrifugally precipitating the colloidal quantum dots to obtain micro colloidal quantum dots and large colloidal quantum dots;
heavily doping the large-size colloidal quantum dots so that the doping ions fill blank conduction bands in the large-size colloidal quantum dots; the volume ratio of the doped ions to the large-size colloidal quantum dots is 1:9-1:4, and the doped substances comprise any one or more of iodine, europium elements, erbium elements or phosphorus elements;
and mixing the doped large-size colloidal quantum dots with the micro colloidal quantum dots to obtain mixed colloidal quantum dots, and manufacturing the mixed colloidal quantum dots into the colloidal quantum dot film according to a preset mode.
Optionally, the manufacturing the mixture colloidal quantum dots into the colloidal quantum dot film according to a preset mode includes:
controlling the flow rate of the cleaning solution to be 1-2.5m/s, so that the cleaning solution washes impurities on the surface of the substrate, and drying the cleaned substrate by using a drying device outputting inert gas;
activating the dried substrate surface by using a plasma cleaning machine in an oxygen atmosphere to activate the substrate surface;
heating the mixed colloidal quantum dots to be in a liquid state, conveying the liquid colloidal quantum dots into an evaporator, controlling the temperature in the evaporator to be between 0 and 80 ℃ and the pressure to be between 10 and 60Kpa, and uniformly spin-coating the liquid colloidal quantum dots onto a substrate which is distributed in advance by using a spin coating machine to form the colloidal quantum dot film;
the evaporator is filled with inert gas, and the inert gas comprises one or more of argon (Ar), helium (He), neon (Ne), krypton (Kr), xenon (xe) and radon (Rn).
Optionally, after the mixture colloidal quantum dots are manufactured into the colloidal quantum dot film according to a preset mode, the method further includes:
doping silver ions with a certain concentration on the surface of the colloidal quantum dot film, and standing for 30-60 min;
evaporating a passivation layer on the doped colloidal quantum dot film, wherein the passivation layer is made of an infrared transparent material;
controlling the thickness of the passivation layer to be within the range of 1um-5 um;
wherein the infrared transparent material comprises any one or more of silicon dioxide, silicon, germanium and calcium fluoride.
Optionally, the number of the colloid quantum dot films in the PN junction is 1-7, and the single-layer thickness is 10nm-50 nm.
Optionally, the micro colloidal quantum dots include colloidal quantum dots with a diameter less than or equal to 4nm, and the large colloidal quantum dots include colloidal quantum dots with a diameter of 5nm to 12 nm.
Optionally, the infrared colloidal quantum dots include any one or more of:
graphene quantum dots, cadmium sulfide quantum dots, and molybdenum disulfide quantum dots.
In a second aspect, a molecular material component for use in a high sensitivity photodetector, the component comprising:
the colloidal quantum dot film is used for manufacturing a P-type surface incidence window layer of the photoelectric detector, and the single-layer thickness of the colloidal quantum dot film is 10nm-50nm (for example, 25 nm);
the isolation layer is arranged between the P-type surface incidence window layer and the intrinsic absorption layer, and comprises a metal oxide thin film;
an N-type intrinsic absorber layer comprising a semiconductor material, the intrinsic absorber layer having a thickness of 2nm to 17nm (e.g., 10.5 nm).
Optionally, the colloidal quantum dot film comprises a film made of heavily doped colloidal quantum dots, and the surface of the colloidal quantum dot film is doped with silver ions;
the number of layers of the colloidal quantum dot film in the PN junction is 1-7, gaps of 1um-5um are formed between single layers of the colloidal quantum dot film in each layer, an isolation layer covers the surface of each layer of the colloidal quantum dot film, and the thickness of each isolation layer is 1um-5um (for example, 2.5 nm);
wherein the colloidal quantum dots constituting the colloidal quantum dot thin film have a diameter of 4nm to 12nm (e.g., 9 nm);
the colloidal quantum dots are any one or more of the following: graphene quantum dots, cadmium sulfide quantum dots, and molybdenum disulfide quantum dots.
In the embodiment of the application, by improving a manufacturing method of a PN molecular material applied to a high-sensitivity photoelectric detector, a colloid quantum dot film is manufactured according to a preset mode and is used as a P-type surface incidence window layer of a PN junction. The sensitivity of the P-type surface incidence window layer to photon induction is improved. And the N-type intrinsic absorption layer is spin-coated by using metal oxide, namely, a metal oxide film is additionally arranged between the P-type surface incidence window layer and the intrinsic absorption layer, so that moisture and oxygen in the air can be isolated, and the stability of the N-type intrinsic absorption layer is improved. In addition, the thickness of the metal oxide film can be conveniently controlled by spin coating. The PN junction formed by the P-type surface incidence window layer and the semiconductor channel layer manufactured by the colloid quantum dot film can generate a built-in electric field, so that the service life of a photon-generated carrier is prolonged, and the photoelectric effect is enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a PN junction applied to a photodetector according to an embodiment of the present disclosure;
FIG. 2 is a schematic flow chart of a method for fabricating a molecular material component according to an embodiment of the present disclosure;
FIG. 3 is a schematic flow chart of another method for fabricating a component of molecular material according to an embodiment of the present disclosure;
fig. 4 is a schematic structural diagram of a photodetector according to an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The terms "first," "second," and the like in the description and claims of the present application and in the above-described drawings are used for distinguishing between different objects and not for describing a particular order. Furthermore, the terms "include" and "have," as well as any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the application. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
Currently, although studies on Colloidal Quantum Dots (CQDs) are being conducted, since CQDs rely on interband absorption of light, there is a high demand for the energy of incident photons to achieve excitation of electrons. And many QDs technologies are concerned with the fact that lead and mercury are not only toxic, but also subject to international regulations on the restriction of hazardous substances, and also cause environmental pollution. How to improve the production process of CQDs, make it exert its advantage when applying to the photodetector, at the same time, overcome its deficiency.
In view of the above problems, embodiments of the present application provide a molecular material component applied to a high-sensitivity photodetector and a method for manufacturing the same. The following detailed description is made with reference to the accompanying drawings.
First, please refer to fig. 1, which shows a schematic structural diagram 100 of a molecular material component applied to a high-sensitivity photodetector, which includes a P-type surface incident window layer 110, an isolation layer 120, and an intrinsic absorption layer 130.
The photoconductive detector has wide application in various fields of military and national economy. The infrared radiation sensor is mainly used for ray measurement and detection, industrial automatic control, photometric measurement and the like in visible light or near infrared wave bands; the infrared band is mainly used for missile guidance, infrared thermal imaging, infrared remote sensing and the like. Another application of the photoconductor is its use as a camera tube target. In order to avoid image blurring caused by diffusion of photogenerated carriers, high-resistance polycrystalline materials such as PbS-PRO, Sb2S3 and the like are used for the target surface of the continuous film. All semiconductor materials with appropriate forbidden band widths or impurity ionization energies have photoelectric effect. But the practical device is manufactured with consideration of performance, process, price, and the like. But also the photoelectric effect performance of different materials is different.
Referring to the embodiments of the present application, a molecular material component applied to a high-sensitivity photodetector includes:
the colloidal quantum dot film is used for manufacturing a P-type surface incidence window layer of the photoelectric detector, and the single-layer thickness of the colloidal quantum dot film is 10-50 nm;
the isolation layer is arranged between the P-type surface incidence window layer and the intrinsic absorption layer, and comprises a metal oxide thin film;
the N-type intrinsic absorption layer comprises a semiconductor material, and the thickness of the intrinsic absorption layer is 2nm-17 nm.
In one possible example, the colloidal quantum dot thin film includes a thin film made of heavily doped colloidal quantum dots, and a surface of the colloidal quantum dot thin film is doped with silver ions;
the number of the colloidal quantum dot thin films in the PN junction is 1-7, gaps of 1-5 um are formed between single layers of the colloidal quantum dot thin films in each layer, an isolation layer covers the surface of each layer of the colloidal quantum dot thin film, and the thickness of each isolation layer is 1-5 um;
wherein the diameter of the colloidal quantum dots constituting the colloidal quantum dot film is 4nm-12 nm;
the colloidal quantum dots are any one or more of the following: graphene quantum dots, cadmium sulfide quantum dots, and molybdenum disulfide quantum dots.
Optionally, an anti-reflection film may be further disposed on the upper surface of the P-type surface incident window layer 110, and the anti-reflection film may reduce reflection of incident light and protect the P-type surface incident window layer 110.
The buffer layer is arranged on the upper end face of the intrinsic absorption layer;
manufacturing a dielectric layer, wherein the dielectric layer is arranged on the upper end face of the buffer layer;
the high electron mobility transistor is applied to the photoelectric detector and comprises a grid electrode, a source electrode, a drain electrode, a passivation layer and a grid electrode side wall; the grid electrode is arranged on the upper end face of the dielectric layer, the passivation layer is arranged on the upper end face of the grid electrode, the grid electrode side walls are arranged on two sides of the grid electrode, and the passivation layer and the grid electrode side walls isolate the grid electrode from the source electrode and the drain electrode.
The molecular material component according to the embodiment of the present application may be implemented based on the structural schematic diagram of the molecular material structural component with the architecture illustrated in fig. 1 or the modified architecture thereof.
Referring to fig. 2, fig. 2 is a schematic flow chart of a method for manufacturing a molecular material component applied to a high-sensitivity photodetector, the molecular material component being a PN junction applied to the high-sensitivity photodetector, the molecular material including colloidal quantum dots, which may include, but is not limited to, the following steps:
201. and manufacturing a colloid quantum dot film according to a preset mode, wherein the colloid quantum dot film is used as a P-type surface incidence window layer of the PN junction.
Specifically, the colloidal quantum dots may be infrared Colloidal Quantum Dots (CQDs). Device cost is greatly reduced since it can be synthesized in solution phase and can be directly applied to substrates (including flexible substrates) using drop casting, spin coating and ink jet printing. Therefore, the infrared colloidal quantum dots can be used for manufacturing the colloidal quantum dot film, and the colloidal quantum dot film is used as a P-type surface incidence window layer of the PN junction. The improvement of the mobility of CQDs can be utilized to improve the internal quantum efficiency and the optimization of the photon collection efficiency when the CQDs are applied to the PN junction of the photoelectric sensor.
Optionally, the infrared colloidal quantum dots include any one or more of: graphene quantum dots, cadmium sulfide quantum dots, and molybdenum disulfide quantum dots. Since mercury and lead Quantum Dots (QDs) currently being studied are toxic, although their performance in short and medium waves is superior to other similar QDs, they are limited by international regulations on the restriction of harmful substances and also cause pollution to the environment. Therefore, in the present example, the raw material containing no mercury and lead is selected when the colloidal quantum dots are manufactured, and the quantum dots containing no mercury and lead are manufactured.
202. And manufacturing an N-type intrinsic absorption layer, and spin-coating the N-type intrinsic absorption layer by using metal oxide to obtain the N-type intrinsic absorption layer modified by the metal oxide, wherein the N-type intrinsic absorption layer comprises a semiconductor material.
Specifically, the N-type intrinsic absorption layer and the P-type surface incidence window layer may be complementary infrared colloidal quantum dots. The N-type intrinsic absorber layer may also be doped with P, Si, S and Te related N-type impurities with typical electron concentrations of 1X 1017-1×1021cm3. The thickness of the N-type intrinsic absorption layer is 30nm-60 nm.
In addition, the metal oxide may be any one or more of: stannous oxide, nickel oxide, or aluminum oxide. The thickness of the thin film formed by spin coating the metal oxide is less than or equal to 8 nm.
203. And arranging the colloid quantum dot film on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide by adopting a photoetching process to obtain a PN junction.
Optionally, the number of the colloid quantum dot films in the PN junction is 1-7, and the single-layer thickness is 10nm-50 nm.
Specifically, after the colloid quantum dots are manufactured, the colloid quantum dots are used for manufacturing the film, and the film can be directly manufactured on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide. A photolithographic process may be employed. Spin-coating photoresist on the substrate with the N-type intrinsic absorption layer by using a spin coater, and baking the photoresist for 2-8 min; forming a pattern of a P-type surface incidence window layer of the PN junction on the photoresist through exposure and development; spin-coating a semiconductor solution into the pattern of the P-type surface incidence window layer of the PN junction by using a spin coater; ultrasonically cleaning the substrate coated with the semiconductor solution in acetone for 4-8 min; and annealing the substrate subjected to ultrasonic cleaning to obtain the PN junction. The number of layers of the colloidal quantum dot film can be adjusted according to different application scenes, the range is 1-7 layers, and the single-layer thickness is 10nm-50 nm.
In addition, the colloid quantum dot film can be manufactured firstly, the pattern of the P-type surface incidence window layer of the PN junction is etched by utilizing the photoetching process, and then the film is attached to the pattern, so that the film and the N-type intrinsic absorption layer form the PN junction.
Therefore, in the embodiment of the application, by improving the manufacturing method of the molecular material of the PN applied to the high-sensitivity photodetector, the colloid quantum dot film is manufactured in a preset manner, and the colloid quantum dot film is used as the P-type surface incidence window layer of the PN junction. The sensitivity of the P-type surface incidence window layer to photon induction is improved. And the N-type intrinsic absorption layer is spin-coated by using metal oxide, namely, a metal oxide film is additionally arranged between the P-type surface incidence window layer and the intrinsic absorption layer, so that moisture and oxygen in the air can be isolated, and the stability of the N-type intrinsic absorption layer is improved. In addition, the thickness of the metal oxide film can be conveniently controlled by spin coating. The PN junction formed by the P-type surface incidence window layer and the semiconductor channel layer manufactured by the colloid quantum dot film can generate a built-in electric field, the service life of a photon-generated carrier is prolonged, and the photoelectric effect is enhanced.
Referring to fig. 3, fig. 3 is a schematic flow chart of a method for manufacturing a molecular material component applied to a high-sensitivity photodetector according to an embodiment of the present application, where the molecular material component is a PN junction applied to the high-sensitivity photodetector, and the molecular material includes colloidal quantum dots, and the method may include, but is not limited to, the following steps:
301. manufacturing a colloid quantum dot film according to a preset mode, wherein the colloid quantum dot film is used as a P-type surface incidence window layer of the PN junction;
302. doping silver ions with a certain concentration on the surface of the colloidal quantum dot film, standing for 30-60 min, and evaporating a passivation layer on the doped colloidal quantum dot film, wherein the passivation layer is an infrared transparent material; controlling the thickness of the passivation layer to be within the range of 1um-5 um; wherein the infrared transparent material comprises any one or more of silicon dioxide, silicon, germanium and calcium fluoride.
Specifically, silver ions are doped on the surface of the colloidal quantum dot film, so that the activation of the surface optical property of the colloidal quantum dot film can be improved. The silver ions can also be replaced by other well-performing metal cations.
In addition, a passivation layer is evaporated on the surface of the colloidal quantum dot film, so that the colloidal quantum dot film can be protected. And the passivation layer can generate ligand replacement with the surface of the colloidal quantum dot film, so that the surface defect of the colloidal quantum dot film is compensated, and the quantum efficiency is improved. But requires precise control of the thickness of the passivation layer. If the passivation layer is too thin, there is no passivation effect on the colloidal quantum dot film. In contrast, if the colloidal quantum dot thin film is too thick, interfacial tension may be caused due to lattice mismatch of the colloidal quantum dot thin film and the passivation layer, thereby forming a defect state, which affects optical properties of the colloidal quantum dot thin film. The thickness of the passivation layer is controlled between 1um-5 um. The thickness of the passivation layer can also be calculated according to the size and concentration of the nano-crystal of the colloid quantum dot film and the lattice constants of the passivation layer and the colloid quantum dot.
In addition, the passivation layer may be an infrared transparent material. Wherein the infrared transparent material comprises any one or more of silicon dioxide, silicon, germanium and calcium fluoride. The dark current of the P-type surface incident window layer can be reduced by selecting the infrared transparent material.
303. And manufacturing an N-type intrinsic absorption layer, and spin-coating the N-type intrinsic absorption layer by using metal oxide to obtain the N-type intrinsic absorption layer modified by the metal oxide, wherein the N-type intrinsic absorption layer comprises a semiconductor material.
304. And arranging the colloid quantum dot film on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide by adopting a photoetching process to obtain a PN junction.
Wherein, step 301 refers to step 201, and step 303 and 304 refer to step 202 and 203, which are not described herein again.
Therefore, in the embodiment of the application, by improving the manufacturing method of the molecular material of the PN applied to the high-sensitivity photodetector, the colloid quantum dot film is manufactured in a preset manner, and the colloid quantum dot film is used as the P-type surface incidence window layer of the PN junction. During manufacturing, silver ions are doped on the surface of the colloidal quantum dot film, so that the optical performance of the colloidal quantum dot film can be improved, and the sensitivity of the P-type surface incidence window layer to photon induction is further improved. The size of the passivation layer is accurately controlled, so that the performance of the passivation layer is not reduced when the passivation layer is used for protecting the colloid quantum dot film. The N-type intrinsic absorption layer is spin-coated by metal oxide, namely, a metal oxide film is additionally arranged between the P-type surface incidence window layer and the intrinsic absorption layer, so that moisture and oxygen in the air can be isolated, and the stability of the N-type intrinsic absorption layer is improved. In addition, the thickness of the metal oxide film can be conveniently controlled by spin coating. The PN junction formed by the P-type surface incidence window layer and the semiconductor channel layer manufactured by the colloid quantum dot film can generate a built-in electric field, the service life of a photon-generated carrier is prolonged, and the photoelectric effect is enhanced.
In one possible example, the manufacturing of the colloidal quantum dot thin film in a preset manner includes: preparing a reaction solvent according to a certain proportion, heating the reaction solvent to 300-500 ℃, and injecting an organic precursor into the reaction solvent; decomposing the organic precursor by adopting a high-energy decomposition mode, so that the organic precursor is gasified to generate an active intermediate, wherein the high-energy decomposition mode comprises any one or more of heating decomposition, laser decomposition and plasma reaction decomposition; adjusting the temperature in the reactor so that the active intermediate vapor temperature is higher than the thermodynamic critical reaction temperature value, and forming saturated vapor pressure in the reactor so that the active intermediate spontaneously condenses and nucleates; controlling the temperature within the reactor such that the nuclei aggregate to form microparticles in a heating zone of the reactor and nanocrystals are formed at a temperature; inputting carrier gas flow into the reactor, so that the carrier gas flow transports the nanocrystalline to a low-temperature region of the reactor, and colloidal quantum dots are formed through grain growth and aggregation; and manufacturing the colloidal quantum dots into the colloidal quantum dot film according to a preset process.
Specifically, when the colloidal quantum dot film is manufactured, the colloidal quantum dot is manufactured first. First, a reaction solvent is prepared, and a non-coordinating "green" solvent such as liquid paraffin, oleic acid, and Octadecene (ODE) may be used as the reaction solvent, and the solvent ratio may be adjusted according to the size of the prepared colloidal quantum dot, or the ratio of the solvent to the liquid paraffin may be 3:3: 4. In addition, the reaction solvent can also be prepared into a quantum dot aqueous solution by mixing toluene and UV glue. The colloidal quantum dots prepared in different proportions have different morphological characteristics. In order to ensure that the colloidal quantum dots in the embodiment have good appearance, uniform light emission and better roundness of the quantum dot, the mass ratio of toluene to UV glue in the aqueous solution for dispensing is adjusted to 1: 9. Therefore, the consistency and the luminous uniformity of the quantum dot array are improved, and the sensitivity and the resolution of the colloid quantum dot device can also be improved.
In addition, after the temperature of the reaction solvent is heated to 300-500 ℃, the organic precursor is injected into the reaction solvent. So that the monomer concentration in the reaction solution can reach supersaturation instantly to form explosive nucleation. Heating is a way to decompose the organic precursor at high energy, so that the organic precursor is gasified to generate an active intermediate. The high-energy decomposition mode can also be any one or more of laser decomposition and plasma reaction decomposition.
The temperature in the reactor is adjusted so that the reactive intermediate vapor temperature continues to be above the thermodynamic critical reaction temperature value, but not so high that a saturated vapor pressure is formed in the reactor so that the reactive intermediate spontaneously nucleates condensation. Controlling the temperature within the reactor such that the nuclei aggregate to form microparticles in a heating zone of the reactor and nanocrystals are formed at a temperature. A large amount of monomers are consumed in the nucleation process, so that the concentration of the unreacted monomers is rapidly reduced, and when the concentration is lower than a certain value, a new crystal nucleus is not formed any more, and the growth stage of the crystal nucleus is started to realize the synthesis of the nuclear quantum dots.
In order to improve the speed of grain growth and aggregation, a carrier gas flow is input into the reactor, and the carrier gas flow is inert gas. The reactor is filled with inert gas, the inert gas is continuously input, the instant heated inert gas is ensured to output the nanocrystalline to a low-temperature region by utilizing thermal circulation, and the reactor is still filled with the inert gas. The nano-crystal forms colloid quantum dots through grain growth and aggregation in a low-temperature region of the reactor.
In addition, the organic precursor includes any one or more of: group IV (Si, Ge, GeSn), group II-V (InAs, InSb), group I-VI (Ag2S, Ag2Se) and ternary I-III-VI (CuInS2, CuInSe2, AgBiS2, AgInSe2), and the latest metal halide perovskite QDs such as CsSnI3, CsSnPb1-x, FAPbI3, CsxFA1-xPbI3QDs, etc.
Further, after the colloidal quantum dots are manufactured, the colloidal quantum dots can be manufactured into the colloidal quantum dot film according to a preset process.
Therefore, compared with the preparation by a dry method of vapor phase epitaxy, the colloidal quantum dots prepared by a solution chemical synthesis method have the characteristics of accurate and adjustable size and shape, good monodispersity, narrow spectrum (high optical purity), high photoluminescence quantum yield and the like, which are incomparable to the epitaxial technology. Unlike quantum dots prepared on a substrate by vapor phase epitaxy, colloidal quantum dots are independently synthesized, and thus, chemical treatment and film self-assembly at a later stage can be performed. In addition, the relatively inexpensive, simple and scalable solution preparation method produces nearly defect-free quantum dots with a purity far exceeding that of epitaxially grown in a high vacuum environment.
In one possible example, the manufacturing the colloidal quantum dots into the colloidal quantum dot thin film according to a preset process includes: detecting the size of the colloidal quantum dots, and centrifugally precipitating the colloidal quantum dots to obtain micro colloidal quantum dots and large colloidal quantum dots; heavily doping the large-size colloidal quantum dots so that the doping ions fill blank conduction bands in the large-size colloidal quantum dots; the volume ratio of the doped ions to the large-size colloidal quantum dots is 1:9-1:4, and the doped substances comprise any one or more of iodine, europium elements, erbium elements or phosphorus elements; and mixing the doped large-size colloidal quantum dots with the micro colloidal quantum dots to obtain mixed colloidal quantum dots, and manufacturing the mixed colloidal quantum dots into the colloidal quantum dot film according to a preset mode.
Optionally, the micro colloidal quantum dots include colloidal quantum dots with a diameter less than or equal to 4nm, and the large colloidal quantum dots include colloidal quantum dots with a diameter of 5nm to 12 nm.
In particular, the doped colloidal quantum dots have better performance. However, since larger sized colloidal quantum dots contain more exposed atoms, the doping method is more efficient on larger quantum dots. In fact, for quantum dots less than 4nm in diameter, the 1Se conduction band is almost empty; for quantum dots with the diameter of 4-8 nm, heavy doping can be formed, and a 1Se conduction band can be partially filled; for quantum dots larger than 8nm in diameter, the 1Se conduction band is almost completely filled, filling about 8 electrons per quantum dot. In order to simplify the operation, the colloid quantum dots with the size of 5nm to 12nm are directly used as the large-size colloid quantum dots and are heavily doped together.
In addition, the volume ratio of the iodine to the large-size colloidal quantum dots during doping is set to be 1:9-1:4 according to the doping effect. The specific proportion can be adjusted according to the proportion of the large-size colloidal quantum dots to the micro colloidal quantum dots and the specific doped ions. The doping may be doping of a certain substance or doping of a mixture of a plurality of substances. Because the size of the micro colloidal quantum dots is too small, the doping effect is not ideal, and the micro colloidal quantum dots are not doped in order to simplify the process flow and reduce the waste of resources. The doped large-size colloidal quantum dots and the micro colloidal quantum dots are mixed to obtain mixed colloidal quantum dots, and the mixed colloidal quantum dots are manufactured into the colloidal quantum dot film according to a preset mode.
In addition, the doped substance includes any one or more of iodine, europium (Eu), erbium (Er) or phosphorus (P).
Therefore, the colloid quantum dots with large sizes are selected for doping, and in the heavily doped quantum dots, the filled conduction bands can improve the photon absorption between bands and the in-band absorption, so that the in-band absorption is possible. This means that the larger the quantum dot, the longer the infrared wavelength it can absorb. The performance of the colloidal quantum dots can be effectively improved. And mixing the doped large-size colloidal quantum dots with the micro colloidal quantum dots to obtain mixed colloidal quantum dots, and manufacturing the mixed colloidal quantum dots into the colloidal quantum dot film according to a preset mode. The method simplifies the manufacturing process, improves the utilization rate of raw materials, and is beneficial to improving the performance of the colloidal quantum dot film.
In one possible example, the manufacturing the mixture of colloidal quantum dots into the colloidal quantum dot film according to a preset manner includes: controlling the flow rate of the cleaning solution to be 1-2.5m/s, so that the cleaning solution washes impurities on the surface of the substrate, and drying the cleaned substrate by using a drying device outputting inert gas; activating the dried substrate surface by using a plasma cleaning machine in an oxygen atmosphere to activate the substrate surface; heating the mixed colloidal quantum dots to be in a liquid state, conveying the liquid colloidal quantum dots into an evaporator, controlling the temperature in the evaporator to be between 0 and 80 ℃ and the pressure to be between 10 and 60Kpa, and uniformly spin-coating the liquid colloidal quantum dots onto a substrate which is distributed in advance by using a spin coating machine to form the colloidal quantum dot film; the evaporator is filled with inert gas, and the inert gas comprises any one or more of argon, helium, neon, krypton, xenon and radon.
Specifically, after the mixture colloidal quantum dots are obtained, the mixture colloidal quantum dots are manufactured into the colloidal quantum dot thin film. The mixture of colloidal quantum dots needs to be heated to be liquefied. The heating temperature is usually 60 ℃ to 80 ℃. And then uniformly spin-coating the liquefied colloidal quantum dots on a substrate which is distributed in advance by using a spin coater to form the colloidal quantum dot film.
In addition, the substrate needs to be subjected to an activation treatment in advance. Firstly, cleaning, wherein the flow rate of the cleaning solution is controlled to be 1-2.5m/s, so that the cleaning solution can be used for cleaning impurities on the surface of the substrate. The cleaning solution can be acetone, ethanol and water in sequence. And drying after the cleaning is finished. In order to avoid polluting the substrate during drying, the embodiment of the application selects a drying device outputting inert gas to dry the cleaned substrate. The gas may be heated to a temperature between 0 c and 80 c.
In addition, when the liquefied colloidal quantum dots are uniformly spin-coated on a substrate distributed in advance by using a spin coater, the environment is set in an evaporator, and the temperature in the evaporator is controlled to be between 0 ℃ and 80 ℃ and the pressure is controlled to be between 10Kpa and 60 Kpa. The evaporator is filled with inert gas, and the inert gas comprises any one or more of argon (Ar), helium (He), neon (Ne), krypton (Kr), xenon (xe) and radon (Rn). The substrate and the colloid quantum dots are prevented from being polluted when the spin coating is convenient. And moreover, the colloid quantum dots can be ensured to be kept in a liquidization state during spin coating through temperature control. And when the spin coating is finished, the temperature in the evaporator is timely reduced, so that the colloid quantum dot film is conveniently air-dried.
Therefore, through cleaning and activating the substrate and selecting the environment when the liquid colloidal quantum dots are spin-coated, the manufactured colloidal quantum dot film is guaranteed to have good appearance and is not polluted by the outside.
Optionally, the method further includes: the colloid quantum dot film is prepared by any one or more of the following preparation methods: vapor phase synthesis, sol-gel method, hydrothermal/solvothermal method, reversed micelle method, continuous ion-shell adsorption reaction method, and thermal injection method.
Optionally, after the colloid quantum dot thin film is disposed on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide by using a photolithography process to obtain a PN junction, the method further includes:
the high electron mobility transistor for manufacturing the photoelectric detector comprises: arranging a buffer layer on the other side of the intrinsic absorption layer, arranging a dielectric layer on the other end face of the buffer layer, forming a gate groove on the upper end face of the dielectric layer by adopting a photoetching process, depositing gate metal and a passivation layer on the upper end face of the gate groove, and forming a gate by adopting a photoetching process; forming grid side walls required by a self-alignment process on two sides of the grid by adopting a back-etching process; depositing a source electrode metal layer and a drain electrode metal layer to enable the source electrode metal layer and the drain electrode metal layer to cover the passivation layer and the side wall, forming source electrode and drain electrode contacts in a self-alignment mode, and etching the source electrode metal layer and the drain electrode metal layer to form a source electrode and a drain electrode to obtain the high electron mobility transistor; the source electrode is isolated from the grid electrode through the side wall and the passivation layer, and the drain electrode is isolated from the grid electrode through the side wall and the passivation layer.
Specifically, as shown in fig. 4, the PN junction of the two-terminal device manufactured according to the above embodiment may also be applied to a photodetector by combining a three-terminal device High Electron Mobility Transistor (HEMT), so as to improve the performance of the photodetector. When the HEMT is manufactured, a grid electrode, a source electrode, a drain electrode, a grid electrode dielectric layer, a passivation layer and the like are manufactured by adopting a photoetching process. And manufacturing the grid side wall by adopting a self-alignment process. And the source electrode is isolated from the grid electrode through the side wall and the passivation layer, and the drain electrode is isolated from the grid electrode through the side wall and the passivation layer.
The dielectric layer of the grid electrode comprises a first dielectric layer and/or a second dielectric layer, wherein: the first dielectric layer is SiNx or Al2O3, and the second dielectric layer is SiO 2; the second dielectric layer is positioned on the upper end face of the first dielectric layer. The gate metal may be highly doped T-shaped silicon (Si), and the thickness of the gate metal layer is 150nm-200 nm. The source and drain metal layers are typically a combination of several metals that are alloyed by high temperature annealing to reduce resistance. These metals include Ti, Al, Ni, Au, Ta, TiN, TaN, etc., and are typically deposited layer by metal evaporation or sputtering. The passivation layer may be a silicon nitride and silicon dioxide (SiNx + SiO2) combined material, or may be any one of SiNx and SiO2, or another material containing an insulating substance. The functional requirements of the protective gate and the isolation gate and other components in the high electron mobility transistor are met. The thickness of the passivation layer is 250 nm-700 nm.
In addition, the thickness of the side wall dielectric layer is more than or equal to 200 nm; the preset thickness of the side wall is less than or equal to 50 nm. The direction indicated by the arrow in fig. 4 is the incident direction of light.
Therefore, the HEMT three-terminal device and the PN junction two-terminal device are coupled together in the embodiment of the application, so that the advantages of two-terminal devices are achieved, the three-terminal device is integrated, and the compatibility of the photoelectric detector can be improved. In the HEMT, the parasitic resistance of the HEMT can be further reduced by shortening the distance from the grid to the source and the drain and the size of the three ends, so that the performance of the photoelectric detector applying the HEMT is improved.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the present disclosure has been described with reference to particular embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present disclosure.
Claims (7)
1. A method for manufacturing a molecular material component applied to a high-sensitivity photoelectric detector is characterized in that the molecular material component is a PN junction applied to the high-sensitivity photoelectric detector, the molecular material comprises colloidal quantum dots, and the method comprises the following steps:
manufacturing a colloid quantum dot film according to a preset mode, wherein the colloid quantum dot film is used as a P-type surface incidence window layer of the PN junction;
manufacturing an N-type intrinsic absorption layer, and spin-coating the N-type intrinsic absorption layer by using metal oxide to obtain the N-type intrinsic absorption layer modified by the metal oxide, wherein the N-type intrinsic absorption layer comprises a semiconductor material;
arranging the colloid quantum dot film on the upper surface of the N-type intrinsic absorption layer modified by the metal oxide by adopting a photoetching process to obtain a PN junction;
wherein, according to the colloid quantum dot film of predetermineeing the mode preparation, include:
preparing a reaction solvent according to a certain proportion, heating the reaction solvent to 300-500 ℃, and injecting an organic precursor into the reaction solvent;
decomposing the organic precursor by adopting a high-energy decomposition mode, so that the organic precursor is gasified to generate an active intermediate, wherein the high-energy decomposition mode comprises any one or more of heating decomposition, laser decomposition and plasma reaction decomposition;
adjusting the temperature in the reactor so that the active intermediate vapor temperature is higher than the thermodynamic critical reaction temperature value, and forming saturated vapor pressure in the reactor so that the active intermediate spontaneously condenses and nucleates;
controlling the temperature within the reactor such that the nuclei aggregate to form microparticles in a heating zone of the reactor and nanocrystals are formed at a temperature;
inputting carrier gas flow into the reactor, so that the carrier gas flow transports the nanocrystalline to a low-temperature region of the reactor, and colloidal quantum dots are formed through grain growth and aggregation;
preparing the colloidal quantum dots into the colloidal quantum dot film according to a preset process;
wherein, the colloid quantum dot film is manufactured by the colloid quantum dot according to a preset process, and comprises the following steps:
detecting the size of the colloidal quantum dots, and centrifugally precipitating the colloidal quantum dots to obtain micro colloidal quantum dots and large colloidal quantum dots;
heavily doping the large-size colloidal quantum dots so that doping ions fill blank conduction bands in the large-size colloidal quantum dots; the volume ratio of the doped ions to the large-size colloidal quantum dots is 1:9-1:4, and the doped substances comprise any one or more of iodine, europium elements, erbium elements or phosphorus elements;
mixing the doped large-size colloidal quantum dots with the micro colloidal quantum dots to obtain mixed colloidal quantum dots, and manufacturing the mixed colloidal quantum dots into the colloidal quantum dot film according to a preset mode;
wherein, will the mixed colloid quantum dot makes according to predetermined mode colloid quantum dot film includes:
controlling the flow rate of the cleaning solution to be 1-2.5m/s, so that the cleaning solution washes impurities on the surface of the substrate, and drying the cleaned substrate by using a drying device outputting inert gas;
activating the dried substrate surface by using a plasma cleaning machine in an oxygen atmosphere to activate the substrate surface;
heating the mixed colloidal quantum dots to be in a liquid state, conveying the liquid colloidal quantum dots into an evaporator, controlling the temperature in the evaporator to be between 0 and 80 ℃ and the pressure to be between 10 and 60Kpa, and uniformly spin-coating the liquid colloidal quantum dots onto a substrate which is distributed in advance by using a spin coating machine to form the colloidal quantum dot film;
the evaporator is filled with inert gas, and the inert gas comprises any one or more of argon, helium, neon, krypton, xenon and radon.
2. The method of claim 1, wherein after the mixed colloidal quantum dots are fabricated into the colloidal quantum dot thin film according to a predetermined manner, the method further comprises:
doping silver ions with a certain concentration on the surface of the colloidal quantum dot film, standing for 30-60 min, and evaporating a passivation layer on the doped colloidal quantum dot film, wherein the passivation layer is an infrared transparent material;
controlling the thickness of the passivation layer to be within the range of 1um-5 um;
wherein the infrared transparent material comprises any one or more of silicon dioxide, silicon, germanium and calcium fluoride.
3. The method of claim 1, wherein the number of layers of the colloidal quantum dot thin film in the PN junction is 1-7, and the single-layer thickness is 10nm-50 nm.
4. The method of claim 1, wherein the micro colloidal quantum dots comprise colloidal quantum dots with a diameter of 4nm or less, and the macro-sized colloidal quantum dots comprise colloidal quantum dots with a diameter of 5nm to 12 nm.
5. The method of claim 1, wherein the infrared colloidal quantum dots comprise any one or more of:
graphene quantum dots, cadmium sulfide quantum dots, and molybdenum disulfide quantum dots.
6. A molecular material part for use in a high sensitivity photodetector, wherein the molecular material part is processed by the method of any one of claims 1 to 5, wherein the molecular material part comprises:
the colloidal quantum dot film is used for manufacturing a P-type surface incidence window layer of the photoelectric detector, and the single-layer thickness of the colloidal quantum dot film is 10-50 nm;
the isolation layer is arranged between the P-type surface incidence window layer and the intrinsic absorption layer, and comprises a metal oxide thin film;
the N-type intrinsic absorption layer comprises a semiconductor material, and the thickness of the intrinsic absorption layer is 2nm-17 nm.
7. The molecular material part according to claim 6, wherein the colloidal quantum dot film comprises a film made of heavily doped colloidal quantum dots, and a surface of the colloidal quantum dot film is doped with silver ions;
the number of the colloidal quantum dot thin films in the PN junction of the component is 1-7, gaps of 1-5 um are formed between single layers of the colloidal quantum dot thin films, an isolation layer covers the surface of each colloidal quantum dot thin film, and the thickness of each isolation layer is 1-5 um;
wherein the diameter of the colloidal quantum dots constituting the colloidal quantum dot film is 4nm-12 nm;
the colloidal quantum dots are any one or more of the following: graphene quantum dots, cadmium sulfide quantum dots, and molybdenum disulfide quantum dots.
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