Synthesis method of gold-doped mercury telluride colloidal quantum dots and infrared light detector

Abstract

The invention relates to a synthesis method of gold-doped mercury telluride colloidal quantum dots and an infrared light detector. The synthesis method of the gold-doped mercury telluride colloidal quantum dots comprises the following steps: preparing a mercury precursor solution and a tellurium precursor solution; injecting the tellurium precursor solution into the mercury precursor solution to prepare a mercury telluride quantum dot solution; and adding a chloroauric acid solution into the mercury telluride quantum dot solution to obtain the gold-doped mercury telluride colloidal quantum dot. According to the synthesis method disclosed by the invention, the gold-doped mercury telluride colloidal quantum dots are synthesized by a post-treatment solution method, so that the synthesis threshold of the mercury telluride colloidal quantum dots is greatly simplified, and the mercury telluride colloidal quantum dots are more controllable, quicker and cheaper.

Description

Technical Field

[0001] The invention relates to the field of semiconductor materials and infrared detection technology, and in particular to a synthesis method of gold-doped mercury telluride colloidal quantum dots and an infrared light detector. Background Art

[0002] Infrared photodetectors are widely used in fields such as autonomous driving, security monitoring and atmospheric monitoring. Currently, commercial detectors mainly rely on single-crystal inorganic semiconductors, such as epitaxially grown InGaAs and HgCdTe, but their high manufacturing costs and complex flip-chip bonding processes limit the popularity of their applications. In contrast, colloidal quantum dots are an ideal choice for infrared detectors due to their adjustable band gap, low cost and excellent solution processability, and are compatible with silicon-based electronic devices.

[0003] Mercury telluride colloidal quantum dots have a large body exciton Bohr radius (39.3nm) and a near-zero body band gap, which extends their absorption bandwidth from short-wave infrared to long-wave infrared, and even covers the terahertz region, showing great application prospects. In infrared photodetectors, the lattice doping of mercury telluride quantum dots affects the performance of the device, mainly in the precise regulation of the quantum dot energy levels. However, lattice doping based on mercury telluride quantum dots has not been studied in depth. In particular, the hole transport layer has an extreme lack of p-type doping options, which poses a severe challenge to large-scale applications and potential device construction. Therefore, it is urgent to develop new technologies to expand the lattice doping of mercury telluride quantum dots. Summary of the invention

[0004] The invention provides a synthesis method of gold-doped mercury telluride colloidal quantum dots and an infrared light detector.

[0005] In a first aspect, the present application provides a method for synthesizing gold-doped mercury telluride colloidal quantum dots, comprising the following steps:

[0006] preparing a mercury precursor solution and a tellurium precursor solution;

[0007] injecting the tellurium precursor solution into the mercury precursor solution to prepare a mercury telluride quantum dot solution;

[0008] A chloroauric acid solution is added to the mercury telluride quantum dot solution to obtain the gold-doped mercury telluride colloidal quantum dots.

[0009] The preparation of the mercury precursor solution comprises:

[0010] Mercuric halide and dodecyl mercaptan are added to oleylamine and heated under an inert atmosphere to obtain a mercury precursor solution;

[0011] Wherein, the mercuric halide includes any one or any combination of mercuric chloride, mercuric bromide and mercuric iodide, and preparing the tellurium precursor solution includes:

[0012] Tellurium particles are added to a tri-n-octylphosphine solution, and heated under a nitrogen atmosphere until the particles are completely dissolved to obtain a tri-n-octylphosphine telluride solution; the tri-n-octylphosphine telluride solution is the tellurium precursor solution.

[0013] The mercury precursor solution and the tellurium precursor solution are mixed to prepare a mercury telluride quantum dot solution, comprising:

[0014] The mercury precursor solution and the tellurium precursor solution are mixed, quenched and precipitated, and then a dispersant is added to the precipitate to prepare a mercury telluride quantum dot solution.

[0015] Wherein, the method for preparing the mercury telluride quantum dot solution comprises:

[0016] Mixing the mercury precursor solution and the tellurium precursor solution to obtain a mercury telluride precursor solution;

[0017] Injecting a quenching agent into the mercury telluride precursor solution for quenching, and then adding an anti-solvent to precipitate quantum dots in the mercury telluride precursor solution to obtain mercury telluride quantum dot powder;

[0018] A 3-mercaptopropionic acid oleylamine solution is added to the mercury telluride quantum dot powder to obtain a mercury telluride quantum dot solution; wherein the 3-mercaptopropionic acid oleylamine solution is obtained by mixing 3-mercaptopropionic acid, oleylamine and n-octane according to a preset ratio.

[0019] Wherein, the synthesis method of gold-doped mercury telluride colloidal quantum dots is carried out in an anhydrous and oxygen-free environment.

[0020] The volume of the anti-solvent is 1-5 times the volume of the mercury telluride precursor solution.

[0021] Wherein, the quenching agent includes any one or any combination of n-hexane, n-octane, toluene, tetrachloroethylene, and chloroform;

[0022] The anti-solvent includes any one or any combination of ethanol, methanol, isopropanol, acetone, and acetonitrile.

[0023] Wherein, the concentration of chloroauric acid is 1-100 mg / mL.

[0024] In a second aspect, the present application further provides an infrared light detector, which includes, from bottom to top, a substrate, a bottom electrode, an electron transport layer, a colloidal quantum dot layer, a hole transport layer, and a top electrode;

[0025] Wherein, the colloidal quantum dot layer is prepared by any of the above-mentioned methods for synthesizing gold-doped mercury telluride colloidal quantum dots.

[0026] The implementation of the embodiments of the present invention has the following beneficial effects:

[0027] (1) The embodiment of the present invention synthesizes gold-doped mercury telluride colloidal quantum dots by a post-treatment solution method, which greatly simplifies the synthesis threshold of mercury telluride colloidal quantum dots, making them more controllable, faster, and cheaper, and having higher potential for industrial production.

[0028] (2) The embodiment of the present invention can effectively promote the nucleation of mercury telluride quantum dots by introducing a certain amount of dodecyl mercaptan precursor solution into the mixed precursor solution, so that the synthesized mercury telluride colloidal quantum dots have better morphology and more stable structure, and their optical and electrical properties are improved.

[0029] (3) In the embodiment of the present invention, a certain amount of chloroauric acid is mixed with a mercury telluride colloidal quantum dot solution by a post-treatment solution processing method to perform gold doping, thereby improving the doping efficiency and doping stability of the quantum dots, making it easier to produce gold-doped mercury telluride colloidal quantum dots from the gold-doped mercury telluride colloidal quantum dot solution.

[0030] (4) The gold-doped colloidal quantum dots prepared in the embodiment of the present invention have adjustable size and controllable morphology, and have good monodispersity, high crystallinity, good photoelectric properties, high technical reliability and high processability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1 It is a schematic flow chart of an embodiment of the method for synthesizing gold-doped mercury telluride colloidal quantum dots disclosed in the present invention;

[0033] Figure 2 yes Figure 1 A schematic flow chart of an embodiment of step S2;

[0034] Figure 3 It is a structural schematic diagram of an embodiment of the infrared light detector disclosed in the present invention. DETAILED DESCRIPTION

[0035] Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. Although exemplary embodiments of the present disclosure are shown in the accompanying drawings, it should be understood that the present disclosure can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present disclosure and to be able to fully convey the scope of the present disclosure to those skilled in the art. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present disclosure.

[0036] Various structural schematic diagrams according to embodiments of the present disclosure are shown in the accompanying drawings. These figures are not drawn to scale, and some details are magnified and some details may be omitted for the purpose of clear expression. The shapes of various regions and layers shown in the figures and the relative sizes and positional relationships therebetween are only exemplary, and may deviate in practice due to manufacturing tolerances or technical limitations, and those skilled in the art may further design regions / layers with different shapes, sizes, and relative positions according to actual needs.

[0037] See also Figure 1 , Figure 1 The figure is a flow chart of an embodiment of the synthesis method of gold-doped mercury telluride colloidal quantum dots disclosed in the present invention. The synthesis method of the invention mainly comprises the following steps:

[0038] S1: preparing a mercury precursor solution and a tellurium precursor solution.

[0039] Specifically, the preparation of the mercury precursor solution includes: adding mercuric halide and dodecyl mercaptan to oleylamine, and heating under an inert atmosphere to obtain a mercury precursor solution, wherein the concentration of mercuric halide in the mercury precursor solution is 0.1 to 200 mg / mL, and the concentration of dodecyl mercaptan solution is 0.1 to 200 mg / mL.

[0040] In one embodiment, 276 mg of mercuric chloride and 15 mL of oleylamine are weighed in a three-necked flask, 40-70 uL of dodecyl mercaptan solution is added, and the mixture is heated to 50-120° C., such as 80° C. or 120° C., under an inert atmosphere for 1 hour to obtain a mercury precursor solution. The amount of dodecyl mercaptan solution added may be, for example, 46 uL or 69 uL.

[0041] Specifically, preparing the tellurium precursor solution includes: adding tellurium particles to a tri-n-octylphosphine solution, heating under a nitrogen atmosphere until completely dissolved, to obtain a tri-n-octylphosphine telluride solution; the tri-n-octylphosphine telluride solution is the tellurium precursor solution. The concentration of the tri-n-octylphosphine telluride solution is 0.1 to 200 mg / mL.

[0042] In one embodiment, 2.54 g of tellurium particles are weighed and dissolved in 20 mL of tri-n-octylphosphine solution, heated to 150-210° C., for example, 160° C., under a nitrogen atmosphere and maintained for 4 hours until the tellurium particles are completely dissolved, and cooled to room temperature to obtain a 1 mmol / mL tri-n-octyltellurium phosphine solution, i.e., a tellurium precursor solution.

[0043] S2: injecting the tellurium precursor solution into the mercury precursor solution to prepare a mercury telluride quantum dot solution.

[0044] At a temperature of 120 to 160° C., the mercury precursor solution and the tellurium precursor solution are mixed, quenched, and precipitated, and a dispersant is added to the precipitate to prepare a mercury telluride quantum dot solution. Figure 2 , Figure 2 yes Figure 1 The flowchart of an embodiment of step S2 in the embodiment specifically includes:

[0045] Step S21: mixing the mercury precursor solution and the tellurium precursor solution to obtain a mercury telluride precursor solution.

[0046] In one embodiment, 1 mL of a tellurium precursor solution is injected into a mercury precursor solution, and timing is started. The reaction is stopped after 3 minutes to obtain a mercury telluride precursor solution. The mercury precursor solution contains dodecyl mercaptan and mercuric halide. Under the catalysis of dodecyl mercaptan, the mercuric halide and the tellurium precursor solution react to generate a mercury telluride precursor solution.

[0047] Step S22: injecting a quenching agent into the mercury telluride precursor solution to quench the reaction, and then adding an anti-solvent to precipitate quantum dots in the mercury telluride precursor solution to obtain mercury telluride quantum dot powder.

[0048] A quenching agent is quickly injected into the mercury telluride precursor solution to quench the reaction and the solution is cooled to room temperature in an ice bath. The quenching agent includes any one or any combination of n-hexane, n-octane, toluene, tetrachloroethylene, and chloroform. In one embodiment, 10 mL of tetrachloroethylene solvent may be injected for quenching; or, in another embodiment, 10 mL of n-hexane may be injected for quenching the reaction.

[0049] In one embodiment, stirring is required for a certain period of time after the quenching agent is added, for example, the stirring time may be 1-60 minutes.

[0050] Further, an anti-solvent is added to the quenched solvent to precipitate the quantum dots in the mercury telluride precursor solution to obtain mercury telluride quantum dot powder. The anti-solvent includes any one or any combination of ethanol, methanol, isopropanol, acetone, and acetonitrile. It should be noted that the volume of the anti-solvent is 1-5 times the volume of the mercury telluride precursor solution.

[0051] Specifically, the quenched solution is poured into a centrifuge tube, and 25 mL of an anti-solvent such as anhydrous ethanol or 25 mL of acetone is added to the centrifuge tube for precipitation. The obtained black powder is mercury telluride quantum dot powder.

[0052] Step S23: adding 3-mercaptopropionic acid oleylamine solution to the mercury telluride quantum dot powder to obtain a mercury telluride quantum dot solution; wherein the 3-mercaptopropionic acid oleylamine solution is obtained by mixing 3-mercaptopropionic acid, oleylamine, and n-octane in a preset ratio.

[0053] Specifically, a 3-mercaptopropionic acid oleylamine solution is prepared. In one embodiment, 3-mercaptopropionic acid, oleylamine, and n-octane are mixed in a preset ratio to obtain a 3-mercaptopropionic acid oleylamine solution. For example, 198 ul of 3-mercaptopropionic acid, 1.59 mL of oleylamine, and 43.2 mL of n-octane are mixed to prepare a 3-mercaptopropionic acid oleylamine solution.

[0054] 7 mL of 3-mercaptopropionic acid oleylamine solution was added to the mercury telluride quantum dot powder to prepare a 50 mg / mL mercury telluride quantum dot solution.

[0055] S3: adding chloroauric acid solution to the mercury telluride quantum dot solution to obtain the gold-doped mercury telluride colloidal quantum dots.

[0056] Specifically, chloroauric acid is mixed with the mercury telluride quantum dot solution and stirred for a period of time to obtain stable gold-doped mercury telluride colloidal quantum dots, wherein the concentration of chloroauric acid is 1-100 mg / mL and the stirring time can be, for example, 1-60 min.

[0057] It should be noted that the above-mentioned steps of the method for synthesizing gold-doped mercury telluride colloidal quantum dots of the present application are all carried out in an anhydrous and oxygen-free environment.

[0058] It is understandable that in the process of synthesizing gold-doped mercury telluride colloidal quantum dots, factors such as reaction temperature, mercury halide, quenching agent and antisolvent can be controlled to adjust the absorption spectrum and quantum dot energy level of gold-doped mercury telluride colloidal quantum dots, thereby obtaining gold-doped mercury telluride colloidal quantum dots with better performance. The gold-doped mercury telluride colloidal quantum dots obtained in the present application have good monodispersity and good processability.

[0059] In summary, the present invention synthesizes gold-doped mercury telluride colloidal quantum dots by adopting a post-treatment solution method, and by adjusting the mercury halide, dodecyl mercaptan, quenching agent, antisolvent, reaction temperature, and doping agent added in the post-treatment, the synthesized gold-doped mercury telluride colloidal quantum dots have the characteristics of adjustable size, controllable morphology, good monodispersity, high crystallinity, good photoelectric properties, high technical reliability, and high processability. In the embodiment of the present application, the gold-doped mercury telluride colloidal quantum dots are synthesized by a post-treatment solution method, which greatly simplifies the synthesis threshold of mercury telluride colloidal quantum dots, making them more controllable, faster, cheaper, and having higher potential for industrial production.

[0060] Specifically, the implementation of the embodiments of the present invention has the following beneficial effects:

[0061] (1) The embodiment of the present invention synthesizes gold-doped mercury telluride colloidal quantum dots by a post-treatment solution method, which greatly simplifies the synthesis threshold of mercury telluride colloidal quantum dots, making them more controllable, faster, and cheaper, and having higher potential for industrial production.

[0062] (2) The embodiment of the present invention can effectively promote the nucleation of mercury telluride quantum dots by introducing a certain amount of dodecyl mercaptan precursor solution into the mixed precursor solution, so that the synthesized mercury telluride colloidal quantum dots have better morphology and more stable structure, and their optical and electrical properties are improved.

[0063] (3) In the embodiment of the present invention, a certain amount of chloroauric acid is mixed with a mercury telluride quantum dot solution by a post-treatment solution processing method to perform gold doping, thereby improving the doping efficiency and doping stability of the quantum dots, making it easier to produce gold-doped mercury telluride colloidal quantum dots from the gold-doped mercury telluride colloidal quantum dot solution.

[0064] (4) The gold-doped colloidal quantum dots prepared in the embodiment of the present invention have adjustable size and controllable morphology, and have good monodispersity, high crystallinity, good photoelectric properties, high technical reliability and high processability.

[0065] See also Figure 3 , Figure 3 : is a schematic diagram of the structure of an embodiment of the infrared light detector of the present application, the infrared light detector comprises from bottom to top: a substrate, a bottom electrode, an electron transport layer, a colloidal quantum dot layer, a hole transport layer, and a top electrode; wherein the colloidal quantum dot layer is prepared by the synthesis method of gold-doped mercury telluride colloidal quantum dots described in any of the above embodiments. In this embodiment,

[0066] The colloidal quantum dot layer is gold-doped mercury telluride colloidal quantum dots prepared by the above method, which inherits the characteristics and functions described above and will not be described again.

[0067] Among them, the substrate can be made of materials such as quartz and glass, and is used to support the bottom electrode, electron transport layer, colloidal quantum dot layer, hole transport layer, and top electrode.

[0068] The bottom electrode and top electrode materials are indium tin oxide, gold electrodes and other materials, which are used to connect the positive and negative electrodes to conduct electricity.

[0069] The electron transport layer material can be zinc oxide, tin oxide, bismuth sulfide, bismuth selenide and other materials for transporting electrons.

[0070] The hole transport layer material can be silver telluride, molybdenum oxide, zinc telluride and other materials for transporting holes.

[0071] The algorithm and display provided herein are not inherently related to any particular computer, virtual system or other device. Various general purpose systems can also be used together with the teachings based on this. According to the above description, it is obvious that the structure required for constructing such systems. In addition, the application is not directed to any specific programming language either. It should be understood that various programming languages ​​can be utilized to realize the content of the application described herein, and the description of the specific language above is for the purpose of disclosing the best mode of implementation of the application.

[0072] In the description provided herein, a large number of specific details are described. However, it is understood that the embodiments of the present application can be practiced without these specific details. In some instances, well-known methods, structures and techniques are not shown in detail so as not to obscure the understanding of this description.

[0073] Similarly, it should be understood that in order to streamline the present disclosure and assist in understanding one or more of the various aspects of the application, in the above description of exemplary embodiments of the present application, the various features of the present application are sometimes grouped together into a single embodiment, figure, or description thereof.

[0074] Those skilled in the art will appreciate that the modules in the device in the embodiment can be adaptively changed and arranged in one or more devices different from the embodiment. The modules or units or components in the embodiment can be combined into one module or unit or component, and in addition they can be divided into multiple submodules or subunits or subcomponents. Except that at least some of such features and / or processes or units are mutually exclusive, all features disclosed in this specification (including abstracts and drawings) and all processes or units of any method or device disclosed in this manner can be combined in any combination. Unless otherwise explicitly stated, each feature disclosed in this specification (including accompanying abstracts and drawings) can be replaced by alternative features that provide the same, equivalent or similar purposes.

[0075] Furthermore, those skilled in the art will appreciate that although some embodiments herein include certain features included in other embodiments but not other features, the combination of features from different embodiments is meant to be within the scope of the present application and to form different embodiments.

[0076] It should be noted that the above embodiments illustrate the present application rather than limit the present application. Any reference symbol between brackets should not be constructed as a limitation to the present application. The word "comprising" does not exclude the existence of components or steps not listed in the present application. The word "one" or "an" before a component does not exclude the existence of multiple such components. The present application can be implemented by means of hardware including several different components and by means of a suitably programmed computer. In the embodiments in which several devices are listed, several of these devices can be embodied by the same hardware item. The use of the words first, second, and third, etc. does not indicate any order. These words can be interpreted as names.

Claims

1. A method for synthesizing gold-doped mercury telluride colloidal quantum dots, characterized in that: The following steps are involved: preparing a mercury precursor solution and a tellurium precursor solution; injecting the tellurium precursor solution into the mercury precursor solution to prepare a mercury telluride quantum dot solution; A chloroauric acid solution is added to the mercury telluride quantum dot solution to obtain the gold-doped mercury telluride colloidal quantum dots.

2. The synthesis method according to claim 1, characterized in that A mercury precursor solution is prepared, comprising: Mercuric halide and dodecyl mercaptan are added to oleylamine and heated under an inert atmosphere to obtain a mercury precursor solution; Wherein, the mercuric halide includes any one or any combination of mercuric chloride, mercuric bromide and mercuric iodide.

3. The synthesis method according to claim 1, characterized in that Prepare a tellurium precursor solution, comprising: Tellurium particles are added to a tri-n-octylphosphine solution, and heated under a nitrogen atmosphere until the particles are completely dissolved to obtain a tri-n-octylphosphine telluride solution; the tri-n-octylphosphine telluride solution is the tellurium precursor solution.

4. The synthesis method according to claim 1, characterized in that The mercury precursor solution and the tellurium precursor solution are mixed to prepare a mercury telluride quantum dot solution, comprising: The mercury precursor solution and the tellurium precursor solution are mixed, quenched and precipitated, and then a dispersant is added to the precipitate to prepare a mercury telluride quantum dot solution.

5. The synthesis method according to claim 4, characterized in that The method for preparing the mercury telluride quantum dot solution comprises: Mixing the mercury precursor solution and the tellurium precursor solution to obtain a mercury telluride precursor solution; Injecting a quenching agent into the mercury telluride precursor solution for quenching, and then adding an anti-solvent to precipitate quantum dots in the mercury telluride precursor solution to obtain mercury telluride quantum dot powder; A 3-mercaptopropionic acid oleylamine solution is added to the mercury telluride quantum dot powder to obtain a mercury telluride quantum dot solution; wherein the 3-mercaptopropionic acid oleylamine solution is obtained by mixing 3-mercaptopropionic acid, oleylamine and n-octane according to a preset ratio.

6. The synthesis method according to claim 5, characterized in that The method for synthesizing gold-doped mercury telluride colloidal quantum dots is carried out in an anhydrous and oxygen-free environment.

7. The synthesis method according to claim 5, characterized in that The volume of the anti-solvent is 1 to 5 times the volume of the mercury telluride precursor solution.

8. The synthesis method according to claim 5, characterized in that The quenching agent includes any one or any combination of n-hexane, n-octane, toluene, tetrachloroethylene, and chloroform; The anti-solvent includes any one or any combination of ethanol, methanol, isopropanol, acetone, and acetonitrile.

9. The synthesis method according to claim 1, characterized in that The concentration of the chloroauric acid is 1-100 mg / mL.

10. An infrared light detector, characterized in that: The infrared light detector includes, from bottom to top, a substrate, a bottom electrode, an electron transport layer, a colloidal quantum dot layer, a hole transport layer, and a top electrode; Wherein, the colloidal quantum dot layer is prepared by the synthesis method of gold-doped mercury telluride colloidal quantum dots as described in any one of claims 1 to 9 above.

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