CN111349431B - Core-shell quantum dot and photoelectric device - Google Patents

Core-shell quantum dot and photoelectric device Download PDF

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CN111349431B
CN111349431B CN202010115395.5A CN202010115395A CN111349431B CN 111349431 B CN111349431 B CN 111349431B CN 202010115395 A CN202010115395 A CN 202010115395A CN 111349431 B CN111349431 B CN 111349431B
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core
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light
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CN111349431A (en
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陈超
何明明
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Najing Technology Corp Ltd
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Abstract

The application discloses core-shell quantum dots and optoelectronic devices. Wherein the photoelectric device comprises a quantum dot core and a semiconductor shell layer coated outside the quantum dot core, the quantum dot core can respond to light with a certain wavelength to generate charges, the semiconductor shell layer transmits light and can conduct charges generated by the quantum dot core, the forbidden band width of the material of the semiconductor shell layer is larger than that of the material of the quantum dot core, and the material of the semiconductor shell layer has a charge mobility larger than 1 multiplied by 10 ‑4 cm 2 The semiconductor material of/(V.s), the transmittance of the semiconductor shell layer to the light of 300 nm-1800 nm wave band is more than 50%. Compared with the existing silicon-based photoelectric detector, the photoelectric device has wide detection spectrum range, the photosensitive layer can be prepared by adopting a solution method, the process is simple, and the cost is low; the response sensitivity of the photosensitive layer formed by the core-shell quantum dots to light is higher than that of the existing silicon-based photosensitive material.

Description

Core-shell quantum dot and photoelectric device
Technical Field
The application relates to the technical field of photoelectric detectors, in particular to a core-shell quantum dot and a photoelectric device.
Background
A photodetector refers to a device capable of converting light energy into electrical energy for measurement. The photoelectric detector is widely applied to the fields of industry, agriculture, national defense, scientific education and the like, and particularly widely applied to the fields of image sensors and machine vision.
However, the existing silicon-based photodetectors have a narrow detection range and are not suitable for the infrared region. Thus, photodetectors with broad spectral response are currently being studied.
Disclosure of Invention
It is an object of the present application to provide a core-shell quantum dot suitable for use in an optoelectronic device, which core-shell quantum dot has a varying electrical conductivity under illumination.
It is another object of the present application to provide an optoelectronic device having a broad spectral response range.
To achieve the above object, according to one aspect of the present application, there is provided a core-shell quantum dot comprising a quantum dot core capable of generating electric charges in response to light of a certain wavelength and a semiconductor shell layer capable of transmitting light and conducting the electric charges generated by the quantum dot core, the semiconductor shell layer having a material with a forbidden bandwidth larger than that of the quantum dot core, the semiconductor shell layer having a material with a charge mobility larger than 1×10 -4 cm 2 And (c) a semiconductor material having a transmittance of greater than 50% for light in the 300nm to 1800nm wavelength band.
Further, the quantum dot core comprises at least one of a group II-VI semiconductor material, a group III-V semiconductor material, a group IV-VI semiconductor material, a group III-VI semiconductor material, a group I-III-VI semiconductor material, preferably the quantum dot core is selected from one of CdS, pbS, znS, hgTe.
Further, the absorption spectrum of the quantum dot core is 300 nm-1800 nm.
Further, the material of the semiconductor shell layer is an oxide semiconductor, the oxide semiconductor is selected from zinc oxide-based semiconductor, indium oxide-based semiconductor, tin oxide-based semiconductor, titanium oxide-based semiconductor or nickel oxide-based semiconductor, and preferably, the thickness of the semiconductor shell layer is 2 nm-100 nm.
According to another aspect of the present application, there is provided an optoelectronic device comprising a photoactive layer, a first electrode electrically connected to one end of the photoactive layer, and a second electrode electrically connected to the other end of the photoactive layer, the photoactive layer comprising a plurality of core-shell quantum dots as described above.
Further, the first electrode and the second electrode are arranged on the peripheral side of the photosensitive layer at intervals, or the first electrode and the second electrode are arranged on the upper side or the lower side of the photosensitive layer at intervals at the same time, or the first electrode and the second electrode are respectively arranged on the upper side and the lower side of the photosensitive layer.
Further, the optoelectronic device further comprises an electron transport layer, at least a part of the photosensitive layer is arranged on the electron transport layer, the electron transport layer is in contact with the first electrode and/or the second electrode, and preferably, the electron transport layer is a graphene layer.
Further, the photoelectric device comprises an N-type channel layer and a P-type channel layer which are stacked, at least one part of the photosensitive layer is arranged on the P-type channel layer, and the first electrode and/or the second electrode are/is in contact with the P-type channel layer.
Further, the optoelectronic device further comprises a base layer, at least a part of the photosensitive layer is arranged on the base layer, the optoelectronic device further comprises an encapsulation layer arranged on the photosensitive layer, at least one of the encapsulation layer and the base layer transmits light, and preferably, one of the encapsulation layer and the base layer transmits light and the other reflects light.
Further, the photoelectric device is a photoelectric detector.
Compared with the prior art, the beneficial effect of this application lies in:
(1) Compared with the existing silicon-based photoelectric detector, the photoelectric device of the application uses quantum dots with a core-shell structure as photosensitive materials, and light rays of an infrared light wave band are effectively detected;
(2) The photosensitive layer of the photoelectric device can be prepared by a solution method, such as printing or embossing, and the preparation process is simple and low in cost, and is suitable for large-scale industrial production;
(3) The response sensitivity of the photosensitive layer formed by the core-shell quantum dots to light is higher than that of the existing silicon-based photosensitive material.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a core-shell quantum dot of the present application;
FIG. 2 is a schematic diagram of one embodiment of an optoelectronic device of the present application;
FIG. 3 is a schematic view of another embodiment of an optoelectronic device of the present application;
FIG. 4 is a schematic diagram of another embodiment of an optoelectronic device of the present application;
FIG. 5 is a schematic diagram of another embodiment of an optoelectronic device of the present application;
FIG. 6 is a schematic diagram of another embodiment of an optoelectronic device of the present application;
FIG. 7 is a schematic diagram of another embodiment of an optoelectronic device of the present application;
FIG. 8 is a schematic view of another embodiment of an optoelectronic device of the present application;
FIG. 9 is a schematic diagram of another embodiment of an optoelectronic device of the present application;
FIG. 10 is a schematic view of another embodiment of an optoelectronic device of the present application;
FIG. 11 is a schematic view of another embodiment of an optoelectronic device of the present application;
FIG. 12 is a schematic view of another embodiment of an optoelectronic device of the present application;
FIG. 13 is a schematic diagram of an optoelectronic device;
fig. 14 is a schematic diagram of a semi-finished product of the optoelectronic device.
In the figure: 1. a photosensitive layer; 100. core-shell quantum dots; 101. a quantum dot core; 102. a semiconductor shell layer; 2. a first electrode; 3. a second electrode; 4. a base layer; 5. an electron transport layer; 51. a P-type channel layer; 52. an N-type channel layer; 6. a substrate; 7. an ink printing chamber; 8. a positive electrode; 9. and a negative electrode.
Detailed Description
The present application will be further described with reference to the specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
In the description of the present application, it should be noted that, for the azimuth terms such as terms "center", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., the azimuth and positional relationships are based on the azimuth or positional relationships shown in the drawings, it is merely for convenience of describing the present application and simplifying the description, and it is not to be construed as limiting the specific protection scope of the present application that the device or element referred to must have a specific azimuth configuration and operation, as indicated or implied.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order.
The terms "comprises" and "comprising," along with any variations thereof, in the description and claims of the present application are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements that are expressly listed or inherent to such process, method, article, or apparatus.
The application provides a core-shell quantum dot 100, as shown in fig. 1, comprising a quantum dot core 101 and a semiconductor shell layer 102 coated outside the quantum dot core 101, wherein the quantum dot core 101 can respond to light with a certain wavelength to generate charges, the semiconductor shell layer 102 transmits light and can conduct charges generated by the quantum dot core 101, and the forbidden bandwidth of a material of the semiconductor shell layer 102 is larger than that of a material of the quantum dot core 101.
In the application, the semiconductor shell 102 is made of a light-transmitting semiconductor material with high charge mobility, after the quantum dot core 101 absorbs light energy, electrons in the core are transferred into the semiconductor shell 102, the concentration of electrons in the semiconductor shell 102 is increased, the mobility is increased, namely the conductivity of the core-shell quantum dot 100 is changed, and by utilizing the change, the conversion from an optical signal to an electric signal can be realized, and the response sensitivity is high. Wrapping the semiconductor shell 102 around the quantum dot core 101 is also beneficial to improving the stability of the quantum dot itself.
The quantum dot core 101 may be a core-shell structure including a core and a shell, or may be a shell-less structure. When the quantum dot core 101 is a core-shell structure, it may be a single-layer shell structure or a multi-layer shell structure.
In some embodiments, quantum dot core 101 includes at least one of a group II-VI semiconductor material, a group III-V semiconductor material, a group IV-VI semiconductor material, a group III-VI semiconductor material, a group I-III-VI semiconductor material. It will be appreciated that the foregoing II-VI, III-V, IV-VI, III-VI or I-III-VI semiconductor materials may be doped or undoped with other elements, and that the foregoing II-VI, III-V, IV-VI, III-VI or I-III-VI semiconductor materials may be binary or multi-compound.
For example, the quantum dot core 101 may include at least one of the following semiconductor materials: cdS, cdSe, cdTe, znS, znTe, znSe, hgS, hgSe, hgTe, gaN, gaP, gaAs, inP, inAs, inSe, inSb, pbS, pbSe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, inPAs, cuInS, cuInSe, hgSeTe, cdZnS, cdZnSe, cdZnTe, cdHgSe, cdHgS, hgZnS, cdZnSeS, cdHgZnTe, hgZnSeTe. The quantum dot core 101 can also be a core-shell structure quantum dot such as CdS/ZnS, cdSe/ZnS, or a quantum dot with gradient alloy characteristics such as CdZnSeS. It is to be understood that the above list is not an exhaustive list.
Preferably, the quantum dot core 101 is selected from one of CdS, pbS, znS, hgTe.
Preferably, the material of the semiconductor shell 102 preferably has a charge mobility greater than 1×10 -4 cm 2 The transmittance of the semiconductor shell 102 to light in the 300 nm-1800 nm band is more than 50% for the semiconductor material of/(V.s). Further, the transmittance of the semiconductor shell 102 to light in the 400 nm-1100 nm band is more than 60%.
In some embodiments, the material of the semiconductor shell 102 is an oxide semiconductor. The oxide semiconductor may be a zinc oxide-based semiconductor, an indium oxide-based semiconductor, a tin oxide-based semiconductor, a titanium oxide-based semiconductor, or a nickel oxide-based semiconductor. The oxide semiconductor may be a doped or undoped semiconductor material, and for example, the oxide semiconductor may be silicon indium zinc oxide, silicon zinc tin oxide, zinc oxide, indium zinc oxide, zinc tin oxide, indium oxide, aluminum indium oxide, titanium oxide, nickel oxide, or the like. It is to be understood that the above list is not an exhaustive list.
Preferably, the semiconductor shell 102 is selected from one of zinc oxide, titanium dioxide, nickel oxide.
In some embodiments, the thickness of the semiconductor shell 102 is 2nm to 100nm.
As shown in fig. 2 to 12, the present application provides an optoelectronic device including a photosensitive layer 1, a first electrode 2 electrically connected to one end of the photosensitive layer 1, and a second electrode 3 electrically connected to the other end of the photosensitive layer 1. Wherein the photoactive layer 1 comprises a plurality of core-shell quantum dots 100 as previously described.
The materials of the first electrode 2 and the second electrode 3 may be metals and/or metal compounds, which are not limited in this application.
When light in a certain wavelength range irradiates the photosensitive layer 1, electrons in the core-shell quantum dots 100 in the photosensitive layer 1 are transferred into the semiconductor shell 102 through the transition of electrons in the quantum dot cores 101 under the action of photons, so that the electron or hole mobility of the semiconductor shell 102 is changed, the conductivity of the photosensitive layer 1 is changed, namely, the current between the first electrode 2 and the second electrode 3 is changed, the optical signals are converted into electric signals, and the response sensitivity is improved.
The wavelength range of light to which the photosensitive layer 1 can respond varies according to the material, the size, the core-shell structure of the core-shell quantum dot 100, that is, the wavelength range to which the photosensitive layer 1 can respond can be adjusted by changing the characteristics of the material, the size, the core-shell structure, and the like of the core-shell quantum dot 100. In addition, different core-shell quantum dots 100 may be mixed to form the photosensitive layer 1, so that the response spectrum of the photosensitive layer 1 is enlarged.
In some embodiments, the photosensitive layer 1 response spectrum is 300nm to 1800nm, i.e., the photosensitive layer 1 is responsive to light in the range of 300nm to 1800nm.
The first electrode 2 and the second electrode 3 may be disposed at a circumferential side of the photosensitive layer 1 with a mutual interval as shown in fig. 2; alternatively, the first electrode 2 and the second electrode 3 may be simultaneously disposed on the lower side of the photosensitive layer 1 as shown in fig. 3, and the first electrode 2 and the second electrode 3 are spaced apart from each other; alternatively, the first electrode 2 and the second electrode 3 are simultaneously disposed on the upper side of the photosensitive layer 1 as shown in fig. 4, and the first electrode 2 and the second electrode 3 are spaced apart from each other; alternatively, the first electrode 2 and the second electrode 3 may be disposed on both upper and lower sides of the photosensitive layer 1, respectively, as shown in fig. 5, 6, 7, or 8.
In some embodiments, the first electrode 2 and the second electrode 3 are disposed at a mutual interval on the circumferential side of the photosensitive layer 1, preferably the first electrode 2 is opposite to the second electrode 3. It should be noted that, the "peripheral side of the photosensitive layer 1" as used herein refers to an outer side perpendicular to an upper side or a lower side of the photosensitive layer 1.
In some embodiments, the first electrode 2 and the second electrode 3 are disposed on upper and lower sides of the photosensitive layer 1, respectively, and the first electrode 2 is opposite to the second electrode 3, as shown in fig. 7 or 8. Further, the first electrode 2 and the second electrode 3 completely cover the lower side and the upper side of the photosensitive layer 1, as shown in fig. 7. At least one of the first electrode 2 and the second electrode 3 transmits light. Preferably, one of the first electrode 2 and the second electrode 3 transmits light and the other reflects light.
In some embodiments, the first electrode 2 and the second electrode 3 are disposed on the upper and lower sides of the photosensitive layer 1, respectively, and the first electrode 2 and the second electrode 3 are staggered from each other, as shown in fig. 5 or fig. 6. Further, the outer sides of the first electrode 2 and the second electrode 3 extend outwards to the outer end of the photosensitive layer 1, as shown in fig. 6, and at this time, the effective utilization rate of the core-shell quantum dot 100 of the photosensitive layer 1 is higher.
In some embodiments, the optoelectronic device further comprises a base layer 4, at least a portion of the photoactive layer 1 being disposed on the base layer 4, as shown in fig. 2, 3, 4, 5, 6, 8.
In the embodiment shown in fig. 2, the photosensitive layer 1 is provided on the base layer 4, and the first electrode 2 is provided on the peripheral side of the photosensitive layer 1 opposite to the second electrode 3. Further, the optoelectronic device further comprises an encapsulation layer (not shown) disposed on the photosensitive layer 1, at least one of the encapsulation layer and the base layer 4 being transparent. Preferably, one of the encapsulation layer and the base layer 4 transmits light, and the other reflects light, so that light which is not absorbed can reach the photosensitive layer 1 again after being reflected, thereby being beneficial to improving the utilization rate of the photoelectric device to light. The photosensitive layer 1 may be provided on the base layer 4 by printing, coating, spin coating, or the like.
In the embodiment shown in fig. 3, one end of the photosensitive layer 1 is disposed on the first electrode 2, the other end is disposed on the second electrode 3, and the other part of the photosensitive layer 1 is disposed on the base layer 4. Further, the optoelectronic device further comprises an encapsulation layer (not shown) disposed on the photosensitive layer 1, at least one of the encapsulation layer and the base layer 4 being transparent. Preferably, one of the encapsulation layer and the base layer 4 is light transmissive and the other is light reflective. Preferably, the first electrode 2, the second electrode 3 and the base layer 4 are reflective or transparent. The photosensitive layer 1 may be provided on the underlying layer including the base layer 4, the first electrode 2, and the second electrode 3 by printing, coating, spin coating, or the like.
In the embodiment shown in fig. 4, the photosensitive layer 1 is provided on the base layer 4, and the first electrode 2 and the second electrode 3 are provided on the photosensitive layer 1 at a distance from each other. The optoelectronic device further comprises an encapsulation layer (not shown) arranged on the upper side of the photoactive layer 1, the encapsulation layer being arranged between the first electrode 2 and the second electrode 3, at least one of the encapsulation layer and the base layer 4 being transparent. Preferably, one of the encapsulation layer and the base layer 4 is light transmissive and the other is light reflective. Preferably, the first electrode 2, the second electrode 3 and the encapsulation layer are transparent or reflective. The photosensitive layer 1 may be provided on the base layer 4 by printing, coating, spin coating, or the like.
In the embodiment shown in fig. 5 or 6 or 8, a part of the photosensitive layer 1 is provided on the first electrode 2, the other part of the photosensitive layer 1 is provided on the base layer 4, and the second electrode 3 is provided on the photosensitive layer 1. The optoelectronic device further comprises an encapsulation layer (not shown) arranged on the photoactive layer 1, at least one of the encapsulation layer and the base layer 4 being transparent. Preferably, one of the encapsulation layer and the base layer 4 is light transmissive and the other is light reflective. Preferably, the first electrode 2 and the base layer 4 are both transparent or reflective, and the second electrode 3 and the encapsulation layer are both transparent or reflective. The photosensitive layer 1 may be provided on the underlying layer including the base layer 4 and the first electrode 2 by printing, coating, spin coating, or the like.
In some embodiments, the optoelectronic device further comprises an electron transport layer 5, at least a portion of the photoactive layer 1 being disposed on the electron transport layer 5, the first electrode 2 and/or the second electrode 3 being in contact with the electron transport layer 5. The electron transport layer 5 may serve as a channel for electron transport, facilitating electron transfer from the negative electrode to the positive electrode.
As a preference, both the first electrode 2 and the second electrode 3 are in contact with the electron transport layer 5, as shown in fig. 9 or 10.
As another preferable example, the first electrode 2 is in contact with the electron transport layer 5, the photosensitive layer 1 is disposed on the first electrode 2 and the electron transport layer 5, the second electrode 3 is disposed on the photosensitive layer 1, the first electrode 1 and the second electrode 3 are staggered from each other, and the second electrode 3 is opposite to the electron transport layer 5, at this time, the electron transport layer 5 can promote migration of electrons from one end near the negative electrode to one end near the positive electrode, as shown in fig. 12.
Preferably, the electron transport layer 5 is a graphene layer, and the electron mobility of the graphene layer is high. Further, the optoelectronic device further comprises a substrate 6, the graphene layer being disposed on the substrate 6.
As another preferable example, the electron transport layer 5 includes a P-type channel layer 51 and an N-type channel layer 52 which are stacked, and at least a part of the photosensitive layer 1 is provided on the P-type channel layer 51, that is, the P-type channel layer 51 is in contact with the photosensitive layer 1, as shown in fig. 11. The first electrode 2 and/or the second electrode 3 are in contact with the P-type channel layer 51. Further, the optoelectronic device further comprises a substrate 6, and an n-type channel layer 52 is disposed on the substrate 6.
The P-type channel layer 51 and the N-type channel layer 52 can serve as channels for transporting electrons, so that electrons can be promoted to migrate from the negative electrode to the positive electrode, and certain response is achieved to light. Therefore, even if the photosensitive layer 1 is not provided on the P-type channel layer 51, the photoelectric device can realize photoelectric conversion, that is, the photoelectric device disclosed in fig. 13 has a photosensitive function. The photosensitive layer 1 is arranged on the P-type channel layer 51 of the photoelectric device in fig. 13, so that the photosensitive effect of the photoelectric device in the wave band of 300 nm-1800 nm can be remarkably improved. If the P-type channel layer 51 and the N-type channel layer 52 of the photoelectric device in fig. 13 are replaced by graphene layers, and the photosensitive layer 1 is arranged on the graphene layers, the photosensitive effect of the photoelectric device in two wave bands of 300 nm-450 nm and 1000 nm-1800 nm can be remarkably improved.
In the photoelectric device, the preparation method of the photosensitive layer 1 is a printing method based on a solution, and compared with the photosensitive layer prepared by photoetching and other processes, the preparation method is simple in process and low in cost.
The optoelectronic device of the present application can be, but is not limited to, a photodetector.
The photoelectric device can be applied to an image sensor as a photosensitive structure. For example, the photoelectric device is integrated on a photosensitive chip of an image sensor as a pixel unit.
[ example 1 ]
Preparation of PbS/ZnO core-shell quantum dot
(1) Synthesis of PbS quantum dot cores (diameter 5 nm): 800mg of lead acetate and 1.5mL of oleic acid are added into a three-necked bottle, and after mixing, the three-necked bottle is subjected to multiple degassing/air supplementing treatment by using argon; 2mL of Octadecene (ODE) was added and again degassed/aerated with argon multiple times; the reaction temperature was raised to 100℃and simultaneously 120mg of Hexamethyldisiloxane (HMS) and 10mLODE were added to another three-necked flask, and multiple degassing and argon supplementation treatments were performed; heating the lead acetate solution to 130 ℃, and then adding the HMS solution into the lead acetate solution; reacting for 6 minutes, and then slowly cooling the reaction system to room temperature; centrifuging and purifying for later use.
(2) And coating ZnO shell layers (the thickness is 5 nm) outside the PbS quantum dot cores: the purified PbS quantum dot core was dissolved in 700mL of cetyltrimethylammonium bromide (CTAB), stirred ultrasonically for 30 minutes, 40mL of ascorbic acid, 40mg of zinc nitrate and 30mL of cyclohexanetetramine (HMT) were added in a stirred state, rapidly warmed to 100 ℃, maintained for 30 minutes, and then slowly warmed to 180 ℃ and maintained for 3 hours. The charge mobility of the ZnO material of the shell layer is 8 multiplied by 10 -4 cm 2 And (V.s), and the average transmittance of the light in the wavelength band of 300nm to 1800nm is 90%.
[ example 2 ]
FeS 2 /TiO 2 Preparation of core-shell quantum dots
(1) Synthesis of FeS 2 Quantum dot core (diameter 5 nm): 31.7mg of ferrous chloride (FeCl) was taken 2 ) And 6g of stearylamine (ODA) were added to a three-necked flask a, degassed, then inflated with argon several times; heating to 120 ℃, and stirring for 2 hours; then, 64mg of sulfur powder and 2.5mL of biphenyl (diphene) are added into another three-necked flask B, and the mixture is ultrasonically mixed for 10 minutes; then the mixed solution in the three-necked flask B was added to the three-necked flask A, deaerated, stirred for 30 minutes, then warmed to 220℃for 90 minutes, and then naturally cooled to 100 ℃.
(2) In FeS 2 Quantum dot core coated TiO 2 Shell layer (thickness 5 nm): purified FeS 2 The quantum dot core is dispersed in 200mL of oleic acid, 6mL of tetrabutyl titanate is added after ultrasonic stirring is uniform, heating is carried out to 160 ℃, the temperature is kept for 12 hours, and cooling is carried out to room temperature. TiO of shell layer 2 The charge mobility of the material is 2×10 -4 cm 2 And (V.s), and the average transmittance of the light in the wavelength band of 300nm to 1800nm is 85%.
[ example 3 ]
PbS/TiO 2 Preparation of core-shell quantum dots
(1) Synthesis of PbS quantum dot cores (diameter 5 nm): 20mLODE, 0.5g lead oxide, and 8mL oleic acid were mixed in a three-necked flask, degassed under Ar, and aerated several times; heating to 140 ℃, adding a mixture of 0.3g of thiourea and 0.5g of ODE, and uniformly stirring; continuously maintaining at 140 ℃ for 20min, then turning off heating, and cooling to room temperature; centrifuging and purifying for later use.
(2) Coating TiO 2 Shell layer (thickness 5 nm): dispersing the purified PbS quantum dot core in 200mL of oleic acid, adding 6mL of tetrabutyl titanate after ultrasonic stirring uniformly, heating to 160 ℃ for 12 hours, and cooling to room temperature.
[ example 4 ]
Preparation of a photoelectric detector: providing a substrate with an ink printing cavity 7, wherein an anode 8 and a cathode 9 are manufactured in the ink printing cavity 7 by utilizing evaporation or photoetching technology in advance, and the bottom surface of the ink printing cavity 7 is taken as a base layer as shown in fig. 14; the core-shell quantum dots prepared in example 1 were dissolved in chloroform and ink was printed into the ink printing chamber 7 of the substrate using an inkjet printing process. The structure of the fabricated photovoltaic device can be seen in fig. 2.
[ example 5 ]
Preparation of a photoelectric detector: a substrate having a positive electrode and a negative electrode is provided, and a photosensitive layer is prepared on the substrate by a transfer printing process, wherein the material of the photosensitive layer is the core-shell quantum dot prepared in example 2. The structure of the resulting photovoltaic device is shown in fig. 3.
[ example 6 ]
Preparation of a photoelectric detector: providing a substrate with an ink printing cavity 7, wherein an anode 8 and a cathode 9 are manufactured in the ink printing cavity 7 in advance by utilizing an evaporation or photoetching process, and as shown in fig. 14, the bottom surface of the ink printing cavity 7 is sequentially provided with a substrate, an N-type channel layer and a P-type channel layer from bottom to top; the core-shell quantum dots prepared in example 3 were dissolved in chloroform and ink was printed into the ink printing chamber 7 of the substrate using an inkjet printing process. The structure of the fabricated photovoltaic device can be referred to fig. 11.
[ example 7 ]
Preparation of a photoelectric detector: providing a substrate with an ink printing cavity 7, wherein an anode 8 and a cathode 9 are manufactured in the ink printing cavity 7 in advance by utilizing an evaporation or photoetching process, and the bottom surface of the ink printing cavity 7 is sequentially provided with a substrate and a graphene layer from bottom to top as shown in fig. 14; the core-shell quantum dots prepared in example 3 were dissolved in toluene and ink was printed into the ink printing chamber 7 of the substrate using an inkjet printing process. The structure of the fabricated photovoltaic device can be seen in fig. 9.
[ example 8 ]
Preparation of a photoelectric detector: providing a substrate with an ink printing 7 cavity, wherein an anode 8 and a cathode 9 are manufactured in the ink printing 7 cavity by utilizing an evaporation or photoetching process in advance, and the bottom surface of the ink printing 7 is taken as a substrate as shown in fig. 14; the core-shell quantum dots prepared in example 3 were dissolved in toluene and ink was printed into the ink printing chamber 7 of the substrate using an inkjet printing process. The structure of the fabricated photovoltaic device can be seen in fig. 2.
Comparative example 1
Preparation of a photoelectric detector: providing a substrate with an ink printing cavity 7, wherein an anode 8 and a cathode 9 are manufactured in the ink printing cavity 7 by utilizing evaporation or photoetching technology in advance, and the bottom surface of the ink printing cavity 7 is taken as a base layer as shown in fig. 14; the core-shell quantum dots CdSe/ZnS were dissolved in chloroform and the ink was printed into the ink printing chamber 7 of the substrate using an inkjet printing process.
Comparative example 2
Preparation of a photoelectric detector: a substrate with an ink printing 7 cavity is provided, a positive electrode 8 and a negative electrode 9 are manufactured in the ink printing cavity 7 in advance by utilizing an evaporation or photoetching process, and as shown in fig. 14, the bottom surface of the ink printing cavity 7 is sequentially provided with a substrate and a graphene layer from bottom to top.
[ comparative example 3 ]
Preparation of a photoelectric detector: a substrate with an ink printing cavity 7 is provided, the positive electrode 8 and the negative electrode 9 are manufactured in the ink printing cavity 7 in advance by utilizing an evaporation or photoetching process, and as shown in fig. 14, the bottom surface of the ink printing cavity 7 is sequentially provided with a substrate, an N-type channel layer and a P-type channel layer from bottom to top.
The switching ratio test results of each photodetector at a bias voltage of 2V at a detected wavelength of 1300nm are shown in table 1. The on-off ratio is the ratio of the current passing through the device under the condition of light irradiation and no light irradiation and under the condition of the same specified voltage, and the larger the on-off ratio is, the better the detection sensitivity is.
TABLE 1
As can be seen from the experimental data of table 1, the detection sensitivity of the photoelectric devices prepared using the core-shell quantum dots prepared in examples 1 to 3 was higher than that of the photoelectric devices prepared using the conventional core-shell quantum dots (CdSe/ZnS).
The foregoing has outlined the basic principles, main features and advantages of the present application. It will be appreciated by persons skilled in the art that the present application is not limited to the embodiments described above, and that the embodiments and descriptions described herein are merely illustrative of the principles of the present application, and that various changes and modifications may be made therein without departing from the spirit and scope of the application, which is defined by the appended claims. The scope of protection of the present application is defined by the appended claims and equivalents thereof.

Claims (1)

1. The photoelectric detector is characterized by comprising a base layer, a photosensitive layer, a first electrode electrically connected with one end of the photosensitive layer and a second electrode electrically connected with the other end of the photosensitive layer, wherein the photosensitive layer is directly arranged on the base layer, the first electrode and the second electrode are mutually arranged on the periphery of the photosensitive layer at intervals, the photoelectric device further comprises an encapsulation layer arranged on the upper side of the photosensitive layer, one of the encapsulation layer and the base layer is light-transmitting, the other is light-reflecting, the first electrode, the second electrode and the encapsulation layer are light-transmitting or light-reflecting, the photosensitive layer comprises a plurality of core-shell quantum dots, and the core-shell quantum dots are FeS 2 /TiO 2 Quantum dot core FeS 2 TiO with semiconductor shell layer capable of generating charge in response to light of a certain wavelength 2 Light transmitting and capable of conducting charges generated by the quantum dot core, the forbidden bandwidth of the material of the semiconductor shell layer is larger than that of the material of the quantum dot core, and the material of the semiconductor shell layer is that the charge mobility is larger than 1 multiplied by 10 -4 cm 2 And (c) a semiconductor material having a transmittance of greater than 50% for light in the 300nm to 1800nm wavelength band.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683369A (en) * 2012-04-20 2012-09-19 广东普加福光电科技有限公司 Preparation method and application of quantum dot light conversion film for enhancing ultraviolet response of silicon-based imaging device
CN108376750A (en) * 2018-03-05 2018-08-07 南方科技大学 A kind of preparation method and its semiconductor devices of quantum dot/zinc oxide nucleocapsid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102683369A (en) * 2012-04-20 2012-09-19 广东普加福光电科技有限公司 Preparation method and application of quantum dot light conversion film for enhancing ultraviolet response of silicon-based imaging device
CN108376750A (en) * 2018-03-05 2018-08-07 南方科技大学 A kind of preparation method and its semiconductor devices of quantum dot/zinc oxide nucleocapsid

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