CN112531122B - Tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector and preparation method thereof - Google Patents
Tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector and preparation method thereof Download PDFInfo
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- CN112531122B CN112531122B CN202011212839.3A CN202011212839A CN112531122B CN 112531122 B CN112531122 B CN 112531122B CN 202011212839 A CN202011212839 A CN 202011212839A CN 112531122 B CN112531122 B CN 112531122B
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- H—ELECTRICITY
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- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
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- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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Abstract
The invention relates to a tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector and a preparation method thereof, wherein the tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector comprises the following steps: step 1, snO 2 Growth preparation of the micron line; step 2, utilizing SnO obtained in step 1 2 And preparing the heterojunction photoelectric detector by using the micron line. The tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector tests the photoelectric performance of the tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector, and the tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector has the characteristics of high responsivity, high response speed, good stability, wide response spectrum (response wavelength interval: 200-350 nanometers) and the like, so that the PEDOT designed by the invention is PSS/SnO 2 The heterojunction photoelectric detector has important research and application values.
Description
Technical Field
The invention belongs to the field of photoelectric detectors, and particularly relates to a tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector and a preparation method thereof.
Background
Semiconductor materials, which are important components of new materials, support the development of the electronic information industry. With the rapid development of science and technology, the demand of modern high technology on semiconductor materials is increasing, and the semiconductor market has great development potential. In recent years, wide bandgap semiconductor materials have been extensively studied by researchers at home and abroad, and the main research fields include photoelectric detectors, solar cells, high-power devices and the like.
Ultraviolet light is a general term of a wave band with a wavelength of 10-400 nm in a spectrum, and since the ultraviolet light is found, an ultraviolet detection technology causes extensive research of domestic and foreign researchers. The photoelectric detector is a device capable of converting optical signals into electric signals, wherein the ultraviolet photoelectric detector is widely applied to the fields of missile early warning, space detection, biomedicine, space radio communication and the like. At present, wide band gap semiconductor materials such as diamond, gallium oxide, gallium nitride, zinc oxide, and alloy materials GaAlN, znMgO, etc. have been used for ultraviolet detection. Through investigation, it is found that in the ultraviolet band 250nm-350nm, the bandwidth can be detected only by adjusting the components of GaAlN or ZnMgO to change the bandwidth. But the adjustment of the components can cause the change of the crystal lattice structure, and further cause the formation of a large number of crystal lattice defects in the material, thereby leading to the reduction of the function of the device.
Tin dioxide (SnO) 2 ) As a wide band gap semiconductor material, the band gap is 3.6-4.15 eV at room temperature, and is opposite to the ultraviolet band with the wavelength of 250nm-350 nm. However, from the current reports, there is no report of using SnO 2 The characteristic of intrinsic bandwidth enables ultraviolet detection.
Disclosure of Invention
The invention designs a tin oxide-based p/n junction wide-spectrum ultraviolet photodetector and a preparation method thereof, and solves the technical problem that in the existing design, for an ultraviolet band between 250nm and 350nm, only the bandwidth can be changed by adjusting alloy GaAlN or ZnMgO components, so that the detection can be carried out in the band. But the composition adjustment can cause the change of the lattice structure, and further cause the formation of a large number of lattice defects in the material, and the function of the device is reduced.
In order to solve the technical problems, the invention adopts the following scheme:
a preparation method of a tin oxide-based p/n junction wide-spectrum ultraviolet photodetector comprises the following steps: step 1, snO 2 Growth preparation of the micron line; step 2, utilizing SnO obtained in step 1 2 And preparing the heterojunction photoelectric detector by using the micron line.
Preferably, the step 1 comprises the following sub-steps: firstly, mixing tin dioxide powder and carbon powder, and uniformly grinding the mixture into mixed powder; putting the mixed powder into a reaction container, and putting a clean silicon wafer above the reaction container; heating the mixture in a heating device to a growth temperature at a fixed heating rate, keeping the growth temperature unchanged, and continuously introducing a mixed gas of a protective gas and a reaction gas into the heating device; and placing the clean silicon wafer and the reaction container in the heating device, reducing tin dioxide into steam of simple substance tin by carbon powder, reacting the steam of the simple substance tin with reaction gas, recrystallizing to generate tin dioxide micron lines on the silicon wafer, and obtaining the SnO2 micron lines with high crystallization quality after the growth is finished.
Wherein, the reaction vessel can be corundum. The heating device can be a horizontal tube furnace; before the corundum is put into the horizontal tube furnace, the corundum can be put into the quartz tube firstly, and then the quartz tube is put into the horizontal tube furnace.
Preferably, the mass ratio of the tin dioxide to the carbon powder in the step 1 is 1:0.8 to 1.2.
Preferably, the growth temperature in the step 1 is 900 to 1100 ℃.
Preferably, in the step 1, the protective gas is one of argon or nitrogen, and the reaction gas is oxygen; the protective gas flow is 100-200 sccm, and the reaction gas flow is 0-10 sccm.
Preferably, the growth time of the sample in the step 1 is 30-60min.
Preferably, the step 2 comprises the following sub-steps: selecting a SnO2 micron line with good crystallinity, placing the SnO2 micron line on a clean substrate, and evaporating a metal contact electrode at one end of the SnO2 micron line by using a mask or a photoetching process; then to SnO 2 Dripping PEDOT (PSS) solution on the other end of the micron line, wherein SnO can be well mixed with the PEDOT (PSS) solution 2 Wrapping with micron wires, drying, forming core-shell structure with two different semiconductors, and evaporating metal contact electrode on PEDOT (PSS) by mask or photolithography process to obtain PEDOT (PSS/SnO) 2 A heterojunction photodetector.
Preferably, the metal contact electrode in step 2 is a single-layer metal or a metal composite layer formed by combining a plurality of metals selected from titanium, aluminum, indium, nickel, platinum, gold, silver, molybdenum, tantalum, cobalt and tungsten.
Preferably, in the step 2, the substrate is a rigid substrate or a flexible substrate; the rigid substrate is silicon, quartz glass, sapphire or mica; the flexible substrate is polyimide or polyethylene terephthalate.
A tin oxide base p/n junction broad spectrum ultraviolet photoelectric detector is characterized in that: the method comprises the following steps: substrate, n-type SnO 2 PSS material, and metal contact electrode material prepared on p, n type layer; wherein, single SnO 2 The width of the section of the micron line is 1-15 microns, the thickness of the section is 1-15 microns, the length of the micron line is 0.1-1.5 cm, and the thickness of the PEDOT/PSS organic conductive polymer film is 10-1000 nanometers.
Furthermore, the active region of the tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector is a p/n junction heterostructure, and the n type is SnO 2 And the p type is PEDOT-PSS film.
The tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector and the preparation method thereof have the following beneficial effects:
(1) The tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector tests the photoelectric performance of the tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector, and the tin oxide-based p/n junction wide-spectrum ultraviolet photoelectric detector has the characteristics of high responsiveness, high response speed, good stability, wide response spectrum (response wavelength interval: 200-350 nanometers) and the like, so that the PEDOT designed by the invention is PSS/SnO 2 The heterojunction photoelectric detector has important research and application values.
(2) The wide-spectrum ultraviolet photoelectric detector is of a PN heterojunction structure and has a good rectification effect.
(3) The wide-spectrum ultraviolet photoelectric detector has very high responsivity, and the responsivity can reach 35A/W under the bias of-5V. Due to the fact that the micro-nano device is small in size and close in electrode distance, the transit time of a photon-generated carrier to electrodes at two ends under the action of an electric field is short, and compared with a traditional planar PN heterojunction device, the micro-nano device is high in response speed and response.
(4) The wide-spectrum ultraviolet photoelectric detector has the characteristic of self-driving under the condition of no bias voltage, and the responsivity can reach 50mA/W.
(5) The wide-spectrum ultraviolet photoelectric detector overcomes SnO 2 The self-inherent continuous photoconductive effect and the obvious improvement of the response speed are achieved, and single SnO 2 The minutes of (2) are shortened to 0.2s. One of the reasons for causing the continuous photoconductive effect of the tin dioxide is the adsorption of the surface of the tin dioxide to gas, and since the PEDOT and the PSS are coated on the outer side of the micron line, the adsorption to the gas is reduced, the continuous photoconductive effect of the material is correspondingly improved, and the response time of the device is shortened.
(6) The wide-spectrum ultraviolet photoelectric detector has good stability, can be stored for a long time in a natural environment, and does not influence the performance of the wide-spectrum ultraviolet photoelectric detector.
Drawings
FIG. 1 shows PEDOT: PSS/SnO of the present invention 2 The structure of the heterojunction photoelectric detector is schematic.
Fig. 2 is an SEM picture of a single SnO2 micron line.
FIG. 3 shows PEDOT: PSS/SnO of the present invention 2 I-V curves of the heterojunction photoelectric detector at different wave bands.
FIG. 4 shows PEDOT PSS/SnO of the present invention 2 The responsivity curves of the heterojunction photoelectric detector in different wave bands.
FIG. 5 shows PEDOT: PSS/SnO of the present invention 2 The repeatability curves of the heterojunction photoelectric detector at different wave bands.
FIG. 6 shows PEDOT PSS/SnO of the present invention 2 Response speed curve of heterojunction photodetector.
Detailed Description
The present invention is further described below with reference to fig. 1 to 6:
as shown in figure 1 of the drawings, in which,
example 1:
SnO 2 and (4) preparing the micron line. Firstly, cleaning silicon wafers, and respectively weighing SnO with the mass ratio of 1:1 2 And putting the powder and graphite powder into a mortar, uniformly mixing, and fully grinding for more than 2 hours. Secondly, cleaning a silicon wafer, wherein the specific process is that (1) the silicon wafer is cut into square slices with the size of 2cm multiplied by 2cm, and the used silicon wafer is N-type silicon; (2) putting a silicon wafer intoUltrasonic cleaning is carried out in a beaker by using acetone, alcohol and deionized water in sequence, the cleaning time is 10min, and nitrogen is used for blow-drying after the cleaning is finished; (3) step three, preparing a sample, weighing 3g of uniformly ground mixed powder, putting the powder into a corundum boat, and vertically placing a silicon wafer above the corundum boat; and thirdly, heating the tube furnace, namely putting the quartz tube into the horizontal tube furnace, introducing mixed gas into one end of the quartz tube, wherein the gas flow is Ar:120sccm, O2:2sccm, and the other end is open. The tube furnace was then warmed to 1050 ℃ over 200min and the temperature was kept constant. And fourthly, carrying out an experiment step by step, and putting the corundum boat into a quartz tube to enable the corundum boat to be positioned in a constant-temperature area of the tube furnace. The growth time is 60min, the sample is taken out after the temperature is reduced to the room temperature, and SnO with high crystallization quality can be obtained on a silicon chip 2 Micron line.
PEDOT:PSS/SnO 2 And (3) preparing the heterojunction photoelectric detector. Firstly, cleaning a substrate which is a cut quartz glass sheet, wherein the size of the glass sheet is 1 multiplied by 1 cm, cleaning the substrate for 10min by acetone, alcohol and deionized water in sequence, and drying the substrate by nitrogen after cleaning. Selecting a SnO2 micron line with high crystallization quality, transferring the SnO2 micron line onto a clean quartz glass sheet, evaporating metal indium at one end of the micron line to be used as an electrode, and dripping a proper amount of PEDOT (sodium dodecyl sulfate), namely PSS (sodium dodecyl sulfate) solution on the SnO 2 And (3) covering the other side of the micron line by half of the area of the single micron line, putting the unfinished device into a drying oven, drying and taking out, wherein the area of the unfinished device on the other side of the micron line is the same as that of the single micron line, and the area of the unfinished device on the other side of the single micron line is the same as that of the single micron line, namely the area of the single micron line on the other side of the micron line is the same as that of the single micron line, the unfinished device is put into the drying oven and taken out after being dried, and the PEDOT: and (4) evaporating indium on the PSS film to be used as an electrode, and finishing the preparation of the device.
Example 2:
this example is the same as example 1 except for the following features: in this example, snO with a mass ratio of 5:4 was weighed 2 The powder is fully ground after being mixed with the graphite powder.
Example 3:
this example is the same as example 1 except for the following features: in this example, the tube furnace was heated to 1000 ℃ and the temperature was maintained.
The invention is described above with reference to the accompanying drawings, it is obvious that the invention is not limited to the above embodiments, and it is within the scope of the invention to use various modifications of the inventive method concept and solution, or to directly apply the inventive concept and solution to other applications without modification.
Claims (9)
1. A preparation method of a tin oxide-based p/n junction wide-spectrum ultraviolet photodetector comprises the following steps:
step 1, snO 2 Growth preparation of the micron line;
step 2, utilizing SnO obtained in step 1 2 Preparing a heterojunction photoelectric detector by using the micron line;
the step 2 comprises the following sub-steps: selecting a SnO with good crystallinity 2 Micron line, which is put on clean underlay and metal contact electrode is evaporated on one end of the micron line by using mask or photoetching technology; then to SnO 2 Dropping PEDOT (PSS) solution on the micrometer line to well prepare SnO (stannic oxide) 2 Wrapping with micron wires, drying, forming core-shell structure with two different semiconductors, and evaporating metal contact electrode on PEDOT (PSS) by mask or photolithography process to obtain PEDOT (PSS/SnO) 2 A heterojunction photodetector.
2. The method for preparing a tin oxide-based p/n junction broad-spectrum ultraviolet photodetector as claimed in claim 1, wherein the method comprises the following steps:
the step 1 comprises the following sub-steps:
firstly, mixing tin dioxide powder and carbon powder, and uniformly grinding the mixture into mixed powder;
putting the mixed powder into a reaction container, and putting a clean silicon wafer above the reaction container;
heating the mixture in a heating device to a growth temperature at a fixed heating rate, keeping the growth temperature unchanged, and continuously introducing a mixed gas of a protective gas and a reaction gas into the heating device;
the clean silicon chip and the reaction container are placed in the heating device, the carbon powder reduces the stannic oxide into the steam of simple substance tin, the steam of simple substance tin reacts with the reaction gas again, recrystallization is carried out, and the silicon is heated by the reaction gasTin dioxide micron line is generated on the sheet, and SnO with high crystallization quality can be obtained after the growth is finished 2 Micron line.
3. The method of claim 2, wherein the method comprises:
in the step 1, the mass ratio of the tin dioxide to the carbon powder is 1:0.8 to 1.2.
4. The method of claim 2, wherein the method comprises: the growth temperature in the step 1 is 900-1100 ℃.
5. The method of claim 2, wherein the method comprises: in the step 1, the protective gas is one of argon or nitrogen, and the reaction gas is oxygen; the protective gas flow is 100-200 sccm, and the reaction gas flow is 0-10 sccm.
6. The method of claim 2, wherein the method comprises: the growth time of the sample in the step 1 is 30-60min.
7. The method for preparing a tin oxide-based p/n junction broad-spectrum ultraviolet photodetector as claimed in claim 1, wherein the method comprises the following steps:
the metal contact electrode in the step 2 is a single-layer metal composed of titanium, aluminum, indium, nickel, platinum, gold, silver, molybdenum, tantalum, cobalt and tungsten or a metal composite layer formed by combining a plurality of the metals.
8. The method of claim 1, wherein the method comprises: in the step 2, the substrate is a rigid substrate or a flexible substrate; the rigid substrate is silicon, quartz glass, sapphire or mica; the flexible substrate is polyimide or polyethylene terephthalate.
9. A tin oxide base p/n junction broad spectrum ultraviolet photoelectric detector is characterized in that: the method comprises the following steps: substrate, n-type SnO 2 PSS material, and metal contact electrode material prepared on p, n type layer; wherein, single SnO 2 The width of the section of the micron line is 1-15 microns, the thickness of the section is 1-15 microns, the length of the micron line is 0.1-1.5 cm, and the thickness of the PEDOT/PSS organic conductive polymer film is 10-1000 nanometers.
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| US9685567B2 (en) * | 2012-07-20 | 2017-06-20 | Nutech Ventures | Nanocomposite photodetector |
| US10651409B2 (en) * | 2012-07-20 | 2020-05-12 | Nutech Ventures | Narrowband nanocomposite photodetector |
| CN105244440B (en) * | 2015-09-21 | 2017-09-15 | 长安大学 | A kind of flexible thin film type PEDOT ZnO ultraviolet light detectors and preparation method thereof |
| CN106025080A (en) * | 2016-07-13 | 2016-10-12 | 电子科技大学 | Ultraviolet/visible/infrared responding wide spectral organic detection device |
| CN109698278B (en) * | 2018-12-18 | 2023-07-21 | 哈尔滨工业大学 | Organic-inorganic composite structure self-driven solar blind ultraviolet detector and preparation method thereof |
| CN110416414B (en) * | 2019-08-02 | 2021-05-04 | 华南师范大学 | Ultraviolet detector and preparation method thereof |
| CN111564561B (en) * | 2020-05-07 | 2022-03-29 | 东北师范大学 | PPy/SnO2 heterojunction, application thereof, preparation method thereof and photoelectric detector |
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| JP2003298082A (en) * | 2002-03-28 | 2003-10-17 | Asahi Kasei Corp | Composite semiconductor |
| WO2006107312A1 (en) * | 2004-06-15 | 2006-10-12 | President And Fellows Of Harvard College | Nanosensors |
| WO2012167282A1 (en) * | 2011-06-02 | 2012-12-06 | Brown University | High-efficiency silicon-compatible photodetectors based on ge quantumdots and ge/si hetero-nanowires |
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