CN114256364A - Application of self-PN junction semiconductor nano material as infrared photoelectric detector - Google Patents
Application of self-PN junction semiconductor nano material as infrared photoelectric detector Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The application discloses an application of a self-PN junction semiconductor nano material as an infrared photoelectric detector, which is characterized in that the self-PN junction semiconductor nano material is selected from any one of substances with chemical formulas shown as a formula I; MO xMQ2O4Formula I; wherein, the M is selected from any one of divalent transition metal elements; q is selected from any one of group VIII elements; said x represents MQ2O4The molar ratio of the content of the metal oxide to the content of MO is 1-2.5; the self-PN junction semiconductor nano material is a two-phase polycrystalline structure containing a special-shaped heterojunction. The self-PN junction semiconductor nano material solves the problems of large MO forbidden band width, low photoelectric conversion efficiency, strong absorption of ultraviolet light and the like in the prior art, and has good response as a near infrared photoelectric detectorAnd 4, application prospect.
Description
Technical Field
The application relates to an application of a self-PN junction semiconductor nano material as an infrared photoelectric detector, belonging to the technical field of semiconductor nano materials.
Background
Near infrared light is used as an important component of the electromagnetic spectrum, and has a wide application range, including military navigation, night vision, aerospace, weapon detection, civil optical communication, medical imaging, atmospheric detection, pollution monitoring, meteorological analysis and the like. The photoelectric effect can be further divided into an outer photoelectric effect and an inner photoelectric effect, and the near infrared photoelectric detector mainly comprises a detector based on the outer photoelectric effect and the inner photoelectric effect according to different physical mechanisms. The detector based on the external photoelectric effect is generally a vacuum photoelectric device, such as a vacuum photoelectric tube, a photomultiplier tube, an image intensifier tube, and the like. The product is very suitable for detecting weak light signals and fast pulse weak light signals. However, the disadvantages are also obvious, and a vacuum environment and a high-pressure system are required, so that the device is large in size, poor in flexibility and the like. Compared with an external photoelectric detector, the near infrared photoelectric detector based on the internal photoelectric effect has various types, such as a photoresistor, a photoelectric cell, a photodiode, a phototransistor, and the like. The device has the characteristics of simple structure, small volume, high detection sensitivity, good spectral selectivity and high response speed.
At present, the research focus of the near infrared photoelectric detector is mainly a semiconductor nano material photoelectric detector. The nano material refers to a material with the size of 1-100 nm. The nanometer material has the main characteristics of small size, high surface energy, large proportion of surface atoms and large specific surface area. Thus, it has physical properties that are distinct from macroscopic materials, including surface effects, small-scale effects, and the like. Compared with a near infrared photoelectric detector based on a bulk material and a thin film material, the nano material photoelectric detector has the advantages that: (1) the nano material has small size and accords with the development trend of miniaturization and integration of optoelectronic devices; (2) when the size of the nano material is similar to the wavelength of the near infrared light interacted with the nano material, some peculiar photoelectric phenomena can be caused; (3) the huge specific surface area of the nano material can absorb more near infrared radiation; (4) the nano material has small size, so that the charge transmission time in the detection device is greatly reduced, and the response speed of the detector is greatly improved; (5) the nano material has large resistance, and the dark current of the photoelectric device can be controlled at nano ampere level or even smaller.
In recent years, the research on nano-material near infrared photoelectric detectors has been greatly advanced. The commercial near infrared photoelectric detectors at present are various in types, mainly based on Si-based, Ge-based, InGaAs-based and indium phosphide-based products, so as to meet the requirements of the near infrared photoelectric detectors in different fields. However, the problems and challenges it faces remain numerous, focusing primarily on the following: (1) high-quality material growth technology: the performance of the near-infrared photoelectric detector depends on key parameters such as the appearance, quality, conductivity, size and the like of a material, and the synthesis of the nano material with highly controllable size, appearance and chemical components is one of the main factors limiting the development and application of the nano photoelectric device at present; (2) the photoelectric conversion efficiency improving method comprises the following steps: the absorption efficiency of the detection material to near infrared light is the basis for realizing high-efficiency photoelectric conversion, and the absorption capability of the near infrared light can be greatly improved by adopting a nano-structure material with an ultra-large specific surface area at present, but the requirement of a high-performance near infrared photoelectric detector cannot be met; (3) integration technology of unit detector: the function of the unit near infrared photoelectric detector is very limited, and in order to realize the key technologies such as near infrared imaging and the like, the unit detector needs to be assembled into a detector array, and the difficulty in preparing the detector array is that mature and reliable processing means are needed to realize the processes of accurate transfer, regular wiring and the like of nano materials. At present, only the silicon processing technology is mature, and the integration technology of other semiconductor materials is complex, high in cost and difficult to prepare on a large scale in a short time.
Disclosure of Invention
According to one aspect of the application, the application of the self-PN junction semiconductor nano material as the infrared photoelectric detector is provided, the problems that in the prior art, the forbidden bandwidth of MO (M is selected from any one of divalent transition metal elements) is large, the photoelectric conversion efficiency is not high, and only strong absorption is provided to ultraviolet light are solved through the self-PN junction semiconductor nano material, and the self-PN junction semiconductor nano material has a good application prospect as the near infrared photoelectric detector.
The application of a self-PN junction semiconductor nano material as an infrared photoelectric detector is characterized in that the self-PN junction semiconductor nano material is selected from any one of substances with chemical formulas shown as a formula I;
MO·xMQ2O4formula I;
wherein, the M is selected from any one of divalent transition metal elements;
q is selected from any one of group VIII elements;
said x represents MQ2O4The molar ratio of the content of the metal oxide to the content of MO is 1-2.5;
the self-PN junction semiconductor nano material is a two-phase polycrystalline structure containing a special-shaped heterojunction.
Optionally, the average particle size of the self-PN junction semiconductor nano material is 20-30 nm.
Optionally, in the self-PN junction semiconductor nanomaterial, MO is an N-type semiconductor, MQ2O4The semiconductor structure is a P-type semiconductor, and a PN junction structure is formed between the P-type semiconductor and the N-type semiconductor.
Optionally, the upper limit of the value of x is selected from 1.2, 1.4, 1.6, 1.8, 2 and 2.5; the lower limit is selected from 1, 1.2, 1.4, 1.6, 1.8, 2.
Optionally, the M is selected from any one of Zn, Mn, Fe, Co and Ni;
q is selected from any one of Fe, Co and Ru.
Optionally, the self-PN junction semiconductor nanomaterial is hydrophilic.
Optionally, the preparation method of the self-PN junction semiconductor nanomaterial comprises the following steps:
reacting a raw material I containing a Q source, an M source, an alkali source, a surfactant and water to obtain the semiconductor nano material;
the molar ratio of the Q source to the M source is 1-3.6: 2.4-10;
the source of Q is in moles of Q and the source of M is in moles of M.
Optionally, the temperature of the reaction is 140-200 ℃.
Optionally, the reaction time is 10-16 h.
Optionally, the ratio of the Q source, the M source, the alkali source, the surfactant and the water satisfies:
and (3) Q source: m source: alkali source: surfactant (b): 1-3.6 mmol of water: 2.4-10 mmol: 5 mL-20 mL: 0.2-2 mmol: 30-80 mL;
the source of Q is in moles of Q and the source of M is in moles of M.
Optionally, the ratio of the Q source, the M source, the alkali source, the surfactant and the water satisfies: and (3) Q source: m source: alkali source: surfactant (b): water 1.2 to 2.7 mmol: 2-5 mmol: 15-20 mL: 1.2-2 mmol: 50-80 mL.
Optionally, the molar ratio of the Q source to the M source is 1.2-2.7: 2 to 5.
Optionally, the Q source comprises at least one of Q salts;
the M source comprises at least one of M salts;
the alkali source comprises at least one of alkali solutions;
the surfactant comprises at least one of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, triethanolamine, aspartic acid, glycine, sodium citrate, bovine serum albumin, 1, 3-dialkyl acetone and polyethylene glycol;
the salt containing Q comprises at least one of sulfate containing Q, chloride containing Q and nitrate containing Q;
the M salt comprises at least one of an acetate containing M, a nitrate containing M, a chloride containing M and a sulfate containing M;
the alkali solution comprises at least one of a hydrazine monohydrate solution, an ethylene glycol solution, a sodium hydroxide solution, ammonia water and a triethanolamine solution;
optionally, the concentration of the alkali solution is 10-20 mM.
Optionally, the feedstock I is obtained by: mixing and stirring a Q source, an M source and water, adding a surfactant, stirring II, adding an alkali source, and stirring III to obtain a raw material I;
optionally, the addition rate of the alkali source is 40-80 drops/min.
Optionally, the semiconductor material is a self-PN junction semiconductor nano material obtained by doping VIII group elements with ZnO, the self-PN junction semiconductor nano material can be used as a near infrared photodetector, and the technical problems to be solved are that the ZnO forbidden band width is large, the photoelectric conversion efficiency is not high, and only has strong absorption on ultraviolet light, and the VIII group elements (such as Fe and the like) are doped into the ZnO, so that the forbidden band width is effectively shortened, the photoelectric conversion efficiency is improved, and meanwhile, the absorption intensity of the VIII group elements on near infrared light is remarkably enhanced to serve as an N-type semiconductor; and VIII group elements (such as Fe, Co, Ru and the like) are doped into ZnO to obtain a P-type semiconductor, so that the conventional complex composite mechanism is changed, the complex synthesis step of the PN junction is simplified, and the preparation of the near-infrared self-PN junction by a one-step method is realized.
Optionally, the self-PN junction semiconductor nano material is selected from at least one of substances with a chemical formula shown as a formula II;
ZnO·xZnQ2O4formula II;
wherein Q is selected from any one of group VIII elements;
the value range of x is 1-2.
Optionally, the upper limit of the value of x is selected from 1.2, 1.4, 1.6, 1.8 and 2; the lower limit is selected from 1, 1.2, 1.4, 1.6, 1.8.
Q is selected from any one of Fe, Co and Ru.
Optionally ZnQ in the self PN junction semiconductor nanomaterial2O4The ZnO semiconductor is a P-type semiconductor, the ZnO semiconductor is an N-type semiconductor, and a PN junction structure is formed between the P-type semiconductor and the N-type semiconductor.
Optionally, the average particle size of the self-PN junction semiconductor nano material is 20-30 nm.
Optionally, the self-PN junction semiconductor nanomaterial has an average particle size with an upper limit of 22, 25, 28, or 30nm and a lower limit of 20, 22, 25, or 28 nm.
Optionally, the preparation method of the self-PN junction semiconductor nanomaterial comprises the following steps:
reacting a raw material I containing a Q source, a Zn source, an alkali source, a surfactant and water to obtain the self-PN junction semiconductor nano material;
the molar ratio of the Q source to the Zn source is 0.5-0.8: 1.6;
wherein the Q source is calculated by the mole number of Q, and the Zn source is calculated by the mole number of Zn.
Optionally, the molar ratio of the Q source to the Zn source is 0.6-0.8: 1.6;
optionally, the ratio of the Q source, Zn source, alkali source, surfactant and water is such that:
and (3) Q source: a Zn source: alkali source: surfactant (b): 0.5-0.8 mmol of water: 1.6 mmol: 5-15 mL: 0.2-2 mmol: 30-50 mL;
wherein the Q source is calculated by the mole number of Q, and the Zn source is calculated by the mole number of Zn.
Optionally, the Q source: a Zn source: alkali source: surfactant (b): water 0.6-0.8 mmol: 1.6 mmol: 5-15 mL: 0.2-2 mmol: 40-50 mL.
Optionally, the feedstock I is obtained by: mixing and stirring a Q source, a Zn source and water, adding a surfactant, stirring II, adding an alkali source, and stirring III to obtain the raw material I.
Alternatively, the stirring I is stirred until the Q source and the Zn source are completely dissolved until a color change is observed.
Optionally, the stirring time of stirring I is 1-2 minutes.
Alternatively, the stirring II is stirred until the color of the solution gradually changes from light green to light yellow green.
Optionally, the stirring time of the stirring II is 2-3 minutes
Optionally, the stirring III is stirred until the color of the precipitate changes from blue-green to dark green.
Optionally, the stirring time of the stirring III is 25-35 minutes.
Optionally, the addition rate of the alkali source is 40-80 drops/min.
Optionally, the upper limit of the addition rate of the alkali source is selected from 45, 50, 55, 60 drops/min; the lower limit is selected from 40, 45, 50, 55 drops/min.
The reaction conditions include:
the reaction temperature is 140-200 ℃.
Preferably, the conditions of the reaction include:
the reaction time is 10-16 h.
Optionally, the upper limit of the temperature is selected from 150, 160, 180 or 200 ℃; the lower limit is selected from 140, 150, 160 or 180 ℃.
Optionally, the upper time limit is selected from 12, 14 or 16 h; the lower limit is selected from 10, 12 or 14 h.
The source of Q comprises at least one of a Q salt;
the Zn source comprises at least one of Zn salts;
the alkali source comprises at least one of alkali solutions;
the surfactant comprises at least one of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, triethanolamine, aspartic acid, glycine, sodium citrate, bovine serum albumin, 1, 3-dialkyl acetone and polyethylene glycol.
Optionally, the Q-containing salt comprises at least one of a Q-containing sulfate salt, a Q-containing chloride salt, a Q-containing nitrate salt;
the alkali solution comprises at least one of a hydrazine monohydrate solution, an ethylene glycol solution, a sodium hydroxide solution, ammonia water and a triethanolamine solution;
the alkali solution comprises at least one of a hydrazine monohydrate solution, an ethylene glycol aqueous solution, a sodium hydroxide aqueous solution, ammonia water and a triethanolamine aqueous solution.
Optionally, the concentration of the alkali solution is 10-20M.
As an implementation scheme, the application provides a preparation method of a self-PN junction semiconductor nano material, a high-temperature hydrothermal method is adopted, the semiconductor nano material with the near-infrared self-PN junction is synthesized in one step, and the preparation method has the characteristics of simplicity and easiness in operation, low production cost, capability of greatly simplifying the synthesis steps of the PN junction, capability of realizing large-scale production and the like.
The invention provides a synthesis method of a self-PN junction semiconductor nano material, which is not limited by the method, and the specific technical route is as follows:
first, 1.6mmol of zinc acetate dihydrate (Zn (Ac))2·2H2O), adding a certain amount of sulfate containing VIII group elements (such as ferrous sulfate heptahydrate, manganese sulfate and the like), then adding 30-50 mL of deionized water, adding magnetons, stirring until the solution is completely dissolved, wherein the solution gradually becomes light yellow, then adding a certain amount of trisodium citrate dihydrate, stirring until the solution color is changed from light yellow to light green, and at the moment, slowly adding 5-10 mL of hydrazine monohydrate solution (10mol/L N)2H4·H2O), then, the solution gradually produces blue-green precipitate, after stirring for a period of time, the solution becomes dark blue-green precipitate, a certain amount of reaction solution is taken and placed in the inner container of the reaction kettle, a high-temperature oven is placed, the temperature is set between 140 ℃ and 200 ℃, and the heating time is set between 10h and 16 h.
And after the reaction is cooled to room temperature, removing supernatant, taking the lower product, repeatedly washing the lower product with absolute ethyl alcohol and deionized water for several times, and centrifuging the lower product with a centrifuge at the rotation speed of about 5000-10000rpm for 8-12 min. After centrifugal washing, the obtained sample can be dried for 10-24h in a freeze dryer for later use, or directly dispersed in deionized water and absolute ethyl alcohol and stored in a low-temperature environment for later use.
As an embodiment, the present application provides a self-PN junction semiconductor nanomaterial having a small particle size ranging from about 20 to 30 nm; doping group VIII element with ZnO to obtain; has a polycrystalline structure; has strong absorption to near infrared.
Alternatively, the group VIII element includes any one of Fe, Co, Ru, and the like.
As an embodiment, the present application provides a method for preparing a self-PN junction semiconductor nanomaterial, comprising the steps of:
step 1: firstly, weighing a certain amount of zinc acetate dihydrate (Zn (Ac)2·2H2O), adding a certain amount of sulfate containing VIII group elements into the mixed solution, adding deionized water into the mixed solution, and stirring the mixed solution until the mixed solution is completely dissolved until color change is observed;
step 2: then adding a certain amount of sodium citrate, stirring until the sodium citrate is dissolved, adding a hydrazine monohydrate solution, stirring for a period of time, putting a certain amount of reaction solution into a reaction kettle liner, and putting the reaction kettle liner into a high-temperature oven for high-temperature hydrothermal reaction;
and step 3: the reaction is cooled to room temperature, washed and centrifuged, and after the centrifugal washing is finished, the obtained sample is stored for later use.
Optionally, in step 1: weighing Zn (OAc)2·2H2The adding amount of O is 1.6mmol, the sulfate containing VIII group elements can be ferrous sulfate heptahydrate, manganese sulfate and the like, the adding amount is about 0.5-0.8 mmol, and the volume of the added deionized water is 30-50 mL.
Optionally, in step 1: after the stirring was continued, there was a color change, and the solution gradually changed from pale green to pale yellow green in color.
Optionally, in step 2: the addition amount of the sodium citrate is 0.2 mmol-2 mmol, and the N is2H4·H2The adding amount of O is 5-15 mL, the concentration is 10-20M, the sodium citrate is added until the sodium citrate is stirred until the sodium citrate is dissolved, the color of the sodium citrate gradually changes into light green, and the N is added2H4·H2And slowly adding O, wherein the solution is changed from light green to blue-green precipitate.
Optionally, in step 2: said addition of N2H4·H2And O is stirred for a period of time, and the mixture is poured into a reaction kettle when the color of the precipitate is observed to be changed from blue-green to dark green, wherein the high-temperature hydrothermal reaction temperature is 140-200 ℃, and the reaction time is 10-16 h.
Optionally, in step 3: the solvent used for washing is absolute ethyl alcohol and deionized water, and the washing is carried out for 5-8 times alternately, the centrifugal rotating speed is about 5000-10000rpm, and the centrifugal time is 8-12 min.
Optionally, in step 3: the obtained product can be dried for 10-24h in a freeze dryer for later use, or directly dispersed in deionized water or anhydrous ethanol and stored in low temperature environment for later use.
The self-PN junction semiconductor nano material synthesized by the synthesis route can be used as a near-infrared photoelectric detector.
In the present application, the "self-PN junction" is: the prepared complete material contains both P-type semiconductor and N-type semiconductor, and a space charge region (P-N junction) is formed between the P-type (more dots) and the N-type (more holes) due to concentration difference, so that the directional conduction is realized.
In this application, unless otherwise specified, a numerical range represented by "-" or "-" includes endpoints and values therebetween, for example, "10-20M" or "10 to 20M" includes values between 10M and 20M and between 10M and 20M.
The beneficial effects that this application can produce include:
(1) the application of the self-PN junction semiconductor nano material provided by the application is obtained by utilizing the VIII group element hetero MO (M is selected from any one of divalent transition metal elements), and the problems that in the prior art, the MO forbidden band width is large, the photoelectric conversion efficiency is not high, and only strong absorption is realized on ultraviolet light and the like are solved. The self-PN junction semiconductor nano material has good application prospect as a near infrared photoelectric detector.
(2) According to the application of the self-PN junction semiconductor nano material, the VIII group elements are doped into the self-PN junction semiconductor nano material, the forbidden bandwidth is effectively shortened, the photoelectric conversion efficiency is improved, meanwhile, the absorption intensity of the self-PN junction semiconductor nano material on near infrared light is obviously enhanced, the self-PN junction semiconductor nano material is used as a P-type semiconductor, and therefore a nano composite structure containing a P-N junction is formed together with an N-type semiconductor MO, the previous complex composite mechanism is changed, the complex synthesis steps of PN junctions are simplified, and the one-step preparation of the near infrared self-PN junctions is realized through a high-temperature hydrothermal method.
3) The application of the self-PN junction semiconductor nano material provided by the application can realize the preparation of the self-PN junction semiconductor nano material with a special structure by controlling the molar ratio of the Q source to the MO source, the reaction condition and the amount of the added surfactant.
Drawings
Fig. 1 is a schematic plane structure diagram of a near-infrared self-PN junction in the PN junction semiconductor nanomaterial prepared in example 1.
Fig. 2 is a schematic diagram of a photoelectric conversion mechanism of a near-infrared self-PN junction in the PN junction semiconductor nanomaterial prepared in example 2.
FIG. 3 shows ZnO 2.1ZnFe obtained in example 12O4Near infrared photocurrent response from the PN junction.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
EXAMPLE 1 preparation of self-PN junction semiconductor nanomaterials
Preparation of ZnO.2.1 ZnFe with average particle size of 20nm2O4Near infrared self PN junction (conversion of raw material ratio into FeSO)4·7H2O：Zn(Ac)2·2H2O：N2H4·H2O: trisodium citrate dihydrate: deionized water ═ 1.6 mmol: 3.2 mmol: 20mL of: 1.28 mmol: 80 mL):
first, 1.6mmol of zinc acetate dihydrate (Zn (Ac))2·2H2O), 0.8mmol of sulfur heptahydrate was added theretoFerrous acid (FeSO)4·7H2O), 40mL of deionized water was added, then 0.1858g of trisodium citrate dihydrate (0.64mmol) was added and stirred until the solution changed color from light yellow to light green (stirring time 3min), at which time 10mL of N was slowly added2H4·H2O (10mol/L) (the adding speed is 60 drops/min), stirring for a period of time (the stirring time is 30min, 25mL of reaction solution is placed in a liner of a reaction kettle and is placed in a high-temperature oven, the temperature is 180 ℃, the heating time is 14h, after the reaction is cooled to room temperature, absolute ethyl alcohol and deionized water are used for alternately washing for 3 times, when a centrifugal machine is used for centrifugation, the rotating speed is 10000rpm, the centrifugation is 8min, and the obtained product is stored at low temperature for later use, wherein the schematic diagram of the plane structure of the near infrared self-PN junction in the obtained PN junction semiconductor nano material is shown in figure 1, the formation of the PN junction avoids the combination of electron and hole pairs, and the improvement of the carrier concentration is facilitated.
EXAMPLE 2 preparation of self-PN junction semiconductor nanomaterials
Preparation of ZnO. ZnCo with average particle size of 20nm2O4Near infrared self-PN junction:
first, 1.6mmol of zinc acetate dihydrate (Zn (Ac))2·2H2O), 0.8mmol of CoSO was added thereto4·7H2O, 40mL of deionized water was added, then 0.1858g of trisodium citrate dihydrate were added and stirred until the solution changed color from pale yellow to pale green (stirring time 2min), at which time 10mL of N was slowly added2H4·H2O (10mol/L) (the adding speed is 60 drops/min), after stirring for a period of time (the stirring time is 30min), 25mL of reaction solution is placed in a liner of a reaction kettle and is placed in a high-temperature oven, the temperature is 180 ℃, and the heating time is 14 h. And cooling the reaction to room temperature, alternately washing the reaction product by using absolute ethyl alcohol and deionized water for 3 times, centrifuging the reaction product by using a centrifuge at the rotating speed of 10000rpm for 8min, and storing the obtained product at a low temperature for later use. A schematic diagram of a photoelectric conversion mechanism of a near-infrared self-PN junction in the obtained PN junction semiconductor nanomaterial is shown in fig. 2. Since ZnO and ZnCo2O4The valence band and the conduction band of (2) have a potential difference, and a potential difference between the two and a concentration difference formed by a PN junctionEffectively avoids the recombination of photo-generated electrons and hole pairs and greatly improves the photoelectric conversion efficiency in a near infrared region.
Example 3 ZnO 2.1ZnFe2O4Near infrared photocurrent response of PN junction
ZnO·2.1ZnFe2O4The near infrared photoelectrochemistry of (1) was tested using the electrochemical workstation of CHI660E, a standard three-electrode assembly using a saturated calomel electrode as the reference electrode and a platinum electrode as the counter electrode, respectively. ZnO 2.1ZnFe2O4The nano material is coated on the foamed nickel to be used as a working electrode. Wherein, 0.5M of Na2SO4An aqueous solution is used as the electrolytic solution. The working electrode was first completely soaked in the electrolyte solution for 20 minutes and then tested using an electrochemical workstation. After the three-electrode system normally operates for 100 seconds, the working electrode is irradiated by 1208nm laser for a period of time, and the intensity of generated photocurrent is observed. Viewing ZnO.2.1 ZnFe by switching near infrared laser2O4Response of PN junction to near infrared light.
ZnO 2.1ZnFe as shown in FIG. 32O4The PN junction can generate 10.95 multiplied by 10 under the irradiation of near infrared light-4Photocurrent response of a (control in the figure is a pure foamed nickel substrate, corresponding to Blank in the figure). The semiconductor nano material containing the self PN junction has obvious near infrared photoelectric response capability and great potential for being applied to near infrared photoelectric detectors.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The application of the self-PN junction semiconductor nano material as the infrared photoelectric detector is characterized in that the self-PN junction semiconductor nano material is selected from any one of substances with chemical formulas shown as formula I;
MO·xMQ2O4formula I;
wherein, the M is selected from any one of divalent transition metal elements;
q is selected from any one of group VIII elements;
said x represents MQ2O4The molar ratio of the content of the metal oxide to the content of MO is 1-2.5;
the self-PN junction semiconductor nano material is a two-phase polycrystalline structure containing a special-shaped heterojunction.
2. The use according to claim 1, wherein the self-PN junction semiconductor nanomaterial has an average particle size of 20 to 30 nm;
preferably, in the self-PN junction semiconductor nano material, MO is an N-type semiconductor, MQ2O4The semiconductor structure is a P-type semiconductor, and a PN junction structure is formed between the P-type semiconductor and the N-type semiconductor.
3. Use according to claim 1, wherein said M is selected from any one of Zn, Mn, Fe, Co, Ni;
q is selected from any one of Fe, Co and Ru.
4. The use according to claim 1, wherein said self-PN junction semiconductor nanomaterial is hydrophilic.
5. The use according to claim 1, wherein the preparation method of the self-PN junction semiconductor nanomaterial comprises the following steps:
reacting a raw material I containing a Q source, an M source, an alkali source, a surfactant and water to obtain the semiconductor nano material;
the molar ratio of the Q source to the M source is 1-3.6: 2.4-10;
the source of Q is in moles of Q and the source of M is in moles of M.
6. The use according to claim 5, wherein the reaction temperature is 140 to 200 ℃.
7. The use according to claim 5, wherein the reaction time is 10 to 16 hours.
8. The use according to claim 5, wherein the ratio of the Q source, the M source, the alkali source, the surfactant and the water is such that:
and (3) Q source: m source: alkali source: surfactant (b): 1-3.6 mmol of water: 2.4-10 mmol: 5 mL-20 mL: 0.2-2 mmol: 30-80 mL;
the source of Q is in moles of Q and the source of M is in moles of M.
9. The use of claim 5, wherein the Q source comprises at least one of Q salts;
the M source comprises at least one of M salts;
the alkali source comprises at least one of alkali solutions;
the surfactant comprises at least one of polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, triethanolamine, aspartic acid, glycine, sodium citrate, bovine serum albumin, 1, 3-dialkyl acetone and polyethylene glycol;
the salt containing Q comprises at least one of sulfate containing Q, chloride containing Q and nitrate containing Q;
the M salt comprises at least one of an acetate containing M, a nitrate containing M, a chloride containing M and a sulfate containing M;
the alkali solution comprises at least one of a hydrazine monohydrate solution, an ethylene glycol solution, a sodium hydroxide solution, ammonia water and a triethanolamine solution;
preferably, the concentration of the alkali solution is 10-20 mM.
10. Use according to claim 5, wherein the feedstock I is obtained by: mixing and stirring a Q source, an M source and water, adding a surfactant, stirring II, adding an alkali source, and stirring III to obtain a raw material I;
preferably, the adding rate of the alkali source is 40-80 drops/min.
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