CN117613140B - Oxygen-doped palladium diselenide material, preparation method and application thereof in preparation of photoelectric detector - Google Patents
Oxygen-doped palladium diselenide material, preparation method and application thereof in preparation of photoelectric detector Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 55
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009832 plasma treatment Methods 0.000 claims abstract description 41
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000010894 electron beam technology Methods 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 12
- 238000012546 transfer Methods 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 6
- 230000005669 field effect Effects 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 230000004044 response Effects 0.000 description 20
- 239000010408 film Substances 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000005693 optoelectronics Effects 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 transition metal chalcogenides Chemical class 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 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
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Abstract
The invention provides a preparation method of an oxygen-doped palladium diselenide material, which is characterized by comprising the following specific steps: firstly, evaporating Pd on an inverted Si/SiO 2 substrate by an electron beam evaporation coating instrument in a vacuum cavity in a heating evaporation mode by using an electron beam to obtain a palladium film; then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film; and finally, carrying out O 2 plasma treatment on the palladium diselenide film to obtain the oxygen doped palladium diselenide material. According to the invention, O atoms are doped to the PdSe 2 in an O 2 plasma injection mode, so that the regulation and control of the performance of the PdSe 2 are realized; by regulating the doping amount of O, the p-type transition of the transfer characteristic of the field effect transistor based on the PdSe 2 is realized, and the change has stability.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to an oxygen-doped palladium diselenide material, a preparation method and application thereof in preparation of a photoelectric detector.
Background
Two-dimensional materials, particularly transition metal chalcogenides (TMDCs), are generally considered to be a direction of development in the miniaturization of optoelectronic devices. However, intrinsic TMDCs often suffers from lattice defects and fermi pinning, which result in less than ideal device performance in all aspects.
The two-dimensional material has excellent physical and photoelectric properties and van der Waals integration advantages without being limited by lattice mismatch, so that light sources, light modulators, photodetectors and other novel functionally integrated devices with atomic level dimensions can be realized, and the two-dimensional material is an important content for the development of integrated circuits in the late molar age. PdSe 2 is a near infrared sensitive material which is rarely found in TMDCs family, and has potential application of photoelectric devices. At present, precious metal chalcogenide such as PdSe 2、PtS2 is grown by a chemical vapor deposition method, a magnetron sputtering method and the like from bottom to top, so that the application of the photoelectric device can be realized by low-cost manufacturing. However, the growth process is difficult to control due to a number of parameters, resulting in a material with more surface defects, which will have an adverse effect on its properties, and thus a modification strategy for defects needs to be sought.
There have been studies on modification of noble metal chalcogenides such as palladium diselenide by means of defect engineering and the like, which are constructed by van der Waals stacking with other two-dimensional materials, and surface doping. In addition, studies have been conducted on the performance of palladium diselenide which is left in air for a long period of time, and it has been found that slow oxidation in air causes the device transfer characteristics to gradually change to p-type. There are researches and reports that the performance of the palladium diselenide transistor is improved by treating the palladium diselenide with ozone, however, the method has high cost, large toxicity and poor controllability, and is difficult to realize industrialized application.
Disclosure of Invention
The invention aims to provide an oxygen doped palladium diselenide material, a preparation method and application thereof in preparation of a photoelectric detector, so as to solve the technical problem of improving performance of palladium diselenide modification.
In order to achieve the above purpose, the invention provides a preparation method of an oxygen doped palladium diselenide material, which comprises the following specific steps:
(1) Firstly, evaporating Pd on an inverted Si/SiO 2 substrate by an electron beam evaporation coating instrument in a vacuum cavity in a heating evaporation mode by using an electron beam to obtain a palladium film;
(2) Then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film;
(3) And finally, carrying out O 2 plasma treatment on the palladium diselenide film to obtain the oxygen doped palladium diselenide material.
Preferably, in the step (1), a sensor is arranged in the vacuum cavity and used for controlling the thickness of the vapor deposition palladium to be 3nm.
Preferably, in the step (2), the chemical vapor deposition process conditions are as follows: using a chemical vapor deposition apparatus, a volume flow ratio of 9:1, the interior of the equipment is divided into a first area, a second area and a third area, the set growth temperature is 400 ℃, 600 ℃, the set heating time of the first area is 20 minutes, the set heating time of the second area and the third area is 10 minutes, the first area is heated for 10 minutes, at the moment, the second area and the third area start to be heated, the first area, the second area and the third area simultaneously reach the corresponding set growth temperature, and then the first area, the second area and the third area are insulated for 10 minutes.
Preferably, in the step (3), the process conditions of the O 2 plasma treatment are as follows: the treatment time was 30 minutes using a German DienerATTO plasma cleaner at a pressure of 0.3 mbar.
The invention also provides an oxygen-doped palladium diselenide material which is prepared by the preparation method.
The invention also provides application of the oxygen-doped palladium diselenide material in preparation of a photoelectric detector.
Preferably, the arrayed device is constructed by evaporating gold/titanium electrodes on the surface of the oxygen-doped palladium diselenide material by a mask plate method.
Further preferably, the gold/titanium electrode has a thickness of 50nm.
Further preferably, the channel spacing of the gold/titanium electrodes is 50 μm and the electrode dimensions are 3mm by 3mm.
The invention has the following beneficial effects:
palladium as a noble metal material, growing palladium diselenide by direct chemical vapor deposition results in very low utilization of palladium and poor uniformity of the resulting two-dimensional palladium diselenide. Thus, the present invention selects a completely different process. Firstly, pd is evaporated onto an inverted upper Si/SiO 2 substrate by an electron beam evaporation mode in a vacuum environment of a vacuum cavity through an electron beam evaporation coating instrument, the thickness (3 nm) of the evaporated Pd is controlled through a sensor in the vacuum cavity, then a selenization reaction is carried out on the Pd film through a chemical vapor deposition method to obtain a large-area uniform PdSe 2 film, finally, the palladium diselenide is modified through O 2 plasma treatment, and then 50nm Au electrodes are evaporated on the palladium diselenide through a mask method through an electron beam evaporation mode to form the arrayed palladium diselenide photoelectric detector.
The key point of the invention is that a method for preparing palladium diselenide by a chemical vapor deposition method different from the traditional method is selected, namely a metal post-selenization strategy; and for the palladium diselenide obtained by the method, the palladium diselenide is modified through key operation of O 2 plasma treatment, and the oxygen is used for realizing filling of palladium diselenide vacancies grown by chemical vapor deposition through controlling O 2 plasma treatment parameters, so that the regulation and control of carriers are realized. Compared with other methods such as ozone treatment, the method has higher controllability and lower cost.
According to the invention, O atoms are doped to the PdSe 2 in an O 2 plasma injection mode, so that the regulation and control of the performance of the PdSe 2 are realized; by regulating the doping amount of O, the p-type transition of the transfer characteristic of the field effect transistor based on the PdSe 2 is realized, and the change has stability.
According to the invention, through controlling the treatment time of O 2 plasma, the vacancy filling of the PdSe 2 grown by chemical vapor deposition is realized by utilizing O, and the regulation and control of carriers are realized. After O 2 plasma treatment, the photoelectric response capability, including responsivity and detection rate, of the PdSe 2 -based device are improved by hundreds of times, and the response time is also effectively accelerated. In addition, the carrier transfer characteristics of the transistor can be controllably changed by controlling the O 2 plasma treatment time. Firstly, lattice doping of O atoms on Se vacancies in the PdSe 2 can be realized through O 2 plasma, so that the transfer characteristic of the device is changed from bipolar to p-type; secondly, the effect of surface passivation can be generated, which is similar to adding a dielectric layer on the surface, so that the device is more stable. The two-dimensional material photoelectric device is modified in an O 2 plasma mode, so that the two-dimensional material photoelectric device can be easily expanded to other two-dimensional devices, has the value of universality application, and provides a thought for realizing the design of the high-performance two-dimensional material-based photoelectric device.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
Fig. 1 is a graph showing PdSe 2 characterization before and after O 2 plasma treatment. (a) Schematic top and front views of PdSe 2 folded pentagonal fold structure. (b) schematic illustration of Pd principle of electron beam evaporation. (c) Chemical vapor deposition grows a schematic of PdSe 2. (d) Schematic of a PdSe 2 device treated with O 2 plasma. (e) AFM characterization of PdSe 2 thickness. (f) Raman characterization of PdSe 2 with different durations O 2 plasma. (g) XPS spectra of PdSe 2 before and after treatment with (i) O 2 plasma characterize (g) Pd 3d (h) Se 3d and (i) O1 s.
Fig. 2 is the electrical properties of PdSe 2 field effect transistors before and after O 2 plasma treatment. (a) O 2 plasma treated PdSe 2 FET device schematic; (b) Transfer characteristics of PdSe 2 before and after O 2 plasma treatment; (c) A PdSe 2 device having p-type transfer characteristics; (d) The O 2 plasma treatment produces structural changes in the O doped PdSe 2; (e) An output profile of the intrinsic PdSe 2 device after treatment with (f) O 2 plasma; (g) Transfer characteristics of 0min, (h) 10min and (i) 30min O 2 plasma treated PdSe 2 at different leakage voltages.
Fig. 3 is a comparison of the optoelectronic performance of O 2 plasma treated PdSe 2 and intrinsic PdSe 2 optoelectronic devices. (a) The structure of the PdSe 2 device is schematically shown. (b) The O 2 plasma processes the periodic photoelectric response of the PdSe 2 device and (c) the intrinsic PdSe 2 device to different wavelength lasers. (d) O 2 plasma processes the change relation of the photocurrent of the PdSe 2 device with voltage. (e) Response time profile of PdSe 2 device. Rise/down=3.124 s/2.888s. (f) O 2 plasma treatment PdSe 2 device response time. rise/down=0.100 s/0.235s. The responsivity (g) before and after O 2 plasma treatment was compared with the detection rate (h). (i) O 2 plasma treated PdSe 2 device I-V curve under different wavelength lasers and darkness (j-k) O 2 plasma treated PdSe 2 device was compared to responsivity and detection rate of work in the literature. (l) The O 2 plasma processes the photocurrent of the PdSe 2 device under different wavelength lasers. The lasers were 650nm (8.76 nW/. Mu.m 2)、532nm(2.25nW/μm2)、450nm(5.6nW/μm2) and 405nm (17.4 nW/. Mu.m 2).
FIG. 4 is a DFT calculation for PdSe 2 after O 2 plasma treatment; (a) an energy band structure; (b) DOS; (c) work function.
FIG. 5 is a periodic I-t response of the device before and after O 2 plasma treatment; (a) Intrinsic PdSe 2(b)O2 plasma treated PdSe 2.
FIG. 6 is an optical microscope characterization of various durations of O 2 plasma treatment of PdSe 2; (a) 0min (b) 10min (c) 30min and (d) 60min, magnification of 50×.
FIG. 7 is an AFM characterization of PdSe 2 treated with O 2 plasma for different durations; (a) 0min (b) 10min (c) 30min (d) 60min.
Fig. 8 is a graph showing the response and detection rate of PdSe 2 device after O 2 plasma treatment with four wavelength lasers as a function of light transmittance.
Detailed Description
Embodiments of the invention are described in detail below with reference to the attached drawings, but the invention can be implemented in a number of different ways, which are defined and covered by the claims.
An optoelectronic device based on oxygen doped palladium diselenide material is prepared by the following steps:
(1) Firstly, evaporating Pd on an inverted Si/SiO 2 substrate by an electron beam evaporation coating instrument in a vacuum cavity in a heating evaporation mode by using an electron beam to obtain a palladium film;
(2) Then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film;
(3) Then O 2 plasma treatment is carried out on the palladium diselenide film to obtain an oxygen doped palladium diselenide material;
(4) Finally, a mask plate method is adopted to evaporate a gold/titanium electrode on the surface of the oxygen doped palladium diselenide material to construct an arrayed device.
In the step (1), a sensor is arranged in the vacuum cavity and used for controlling the thickness of the vapor deposition palladium to be 3nm.
In the step (2), the chemical vapor deposition process conditions are as follows: using a chemical vapor deposition apparatus, a volume flow ratio of 9:1, the interior of the equipment is divided into a first area, a second area and a third area, the set growth temperature is 400 ℃, 600 ℃, the set heating time of the first area is 20 minutes, the set heating time of the second area and the third area is 10 minutes, the first area is heated for 10 minutes, at the moment, the second area and the third area start to be heated, the first area, the second area and the third area simultaneously reach the corresponding set growth temperature, and then the first area, the second area and the third area are insulated for 10 minutes.
In the step (3), the process conditions of the O 2 plasma treatment are as follows: the treatment time was 30 minutes using a German DienerATTO plasma cleaner at a pressure of 0.3 mbar.
In step (4), the thickness of the gold/titanium electrode was 50nm. The channel spacing of the gold/titanium electrodes was 50 μm and the electrode dimensions were 3mm by 3mm.
In fig. 1 (a) shows the structure of PdSe 2, as seen from a front view and a top view, pdSe 2 has a unique folded pentagonal structure, and this structure makes PdSe 2 have in-plane anisotropic characteristics. This anisotropic lattice structure makes PdSe 2 exhibit more interesting electro-optical anisotropy. In FIG. 1, (b) and (c) are methods for producing a PdSe 2 film. Firstly, pd is evaporated onto an inverted upper Si/SiO 2 substrate by an electron beam evaporation coating instrument in a near vacuum environment in an electron beam heating evaporation mode, the thickness (3 nm) of the evaporated Pd is controlled by a sensor in a cavity, and then a selenization reaction is carried out on a Pd film by a chemical vapor deposition method, so that a PdSe 2 film with large area uniformity is obtained. And then, 50nmAu/Ti electrodes are evaporated on the material PdSe 2 through a mask method in an electron beam evaporation mode to form an arrayed device, the prepared PdSe 2 film is characterized through AFM as shown in (d) of fig. 1, and the prepared PdSe 2 can be seen to have a thickness of 18.07nm and a relatively flat surface in (e) of fig. 1.
Raman characterization was performed to illustrate the change in PdSe 2 caused by O 2 plasma treatment. The raman spectra of the O 2 plasma treated PdSe 2 are shown in fig. 1 (f) for different durations. As the treatment duration varies, the raman characteristic peak also varies significantly. After a long period of treatment, peak positions at 890cm -1(Se=O)、830cm-1(Se-O2), and 630cm -1 (pd=o) appear in this order.
Next, the applicant characterized the PdSe 2 elemental composition before and after O 2 plasma treatment using XPS, and the fitting results are shown in fig. 1 (g) - (i). The 3d peak of Pd in intrinsic PdSe 2 contains two, including 3d 5/2 at 337.1eV and 3d 3/2 at 342.5eV, while after 30min O 2 plasma treatment, the energy of Pd 3d peak position is reduced by nearly 1.0eV, 3d 5/2 and 3d 3/2 peaks are shifted to 336.2eV and 341.3eV, respectively, in addition to which Pd 3d spin-orbit splitting peak is widened, the main reason is that the metastable PdO 2(Pd4+ peak at 343.2eV and 338.2eV is enhanced after O 2 plasma treatment, and typical PdO (Pd 2+) peak is generated at 337.0eV and 342.2 eV; it is apparent that a distinct characteristic peak appears at 59.3eV, which is derived from the increase of SeO 2, and in addition, the Se 3d peak position is shifted by 0.2eV, and the energy becomes low. In addition, O produced a peak at 531.2eV, while 532.7eV peak shifted to 533.0eV. XPS results indicate that O is successfully doped into the lattice, forming pd=o bonds.
Next, the applicant prepared an array of PdSe 2 transistors based on O 2 plasma treatment, in comparison to intrinsic PdSe 2 for transistor performance. The correlation results are shown in fig. 2.
Fig. 2 (a) shows a schematic structure of a device, and a source-drain electrode is formed by depositing 50 nm-thick Au/Ti on the surface of PdSe 2, so as to further realize the performance test of the device.
For the transfer characteristic analysis of the device, as in (b) of fig. 2, the 30min O 2 plasma treatment changed the bipolar transfer behavior of intrinsic PdSe 2 to a p-type transfer mechanism (c) of fig. 2, and the on/off current ratio was raised from the initial 10 3 to 10 6, consistent with the XPS test results described above, indicating that O atoms were successfully filled into the lattice Se vacancies (d) of fig. 2. The transfer of carriers changes after the bias is applied due to the electronegativity difference between the O atoms and Se atoms, thereby producing the effect of p-type doping.
Fig. 2 (e) - (f) show the linear relationship of I ds-Vds for devices before and after O 2 plasma treatment, the ability of the drain voltage device to continuously regulate channel conductance and the output characteristics after treatment were significantly changed relative to intrinsic PdSe 2.
Further, with the change in sensitivity of the device to bias voltage after O 2 plasma treatment for 0min, 10min, and 30min, respectively, as shown in FIGS. 2 (g) - (i), the device exhibited stronger p-type conduction behavior as the O 2 plasma treatment time increased. This result may be due to the progressive filling of Se vacancies with O atoms as the duration of the O 2 plasma treatment increases; from the roughness characterization changes exhibited in fig. 6 and 7, it is further illustrated that the long-term O 2 plasma gradually passivates the surface, which effectively suppresses the tunneling current; in addition, O atoms and O 2 are adsorbed with unreacted Se and Pd on the surface to form an amorphous compound, and a layer of oxide is applied to the surface of the PdSe 2, so that the performance stability of the device is improved.
Next, the applicant prepared an arrayed device for PdSe 2 before and after O 2 plasma treatment, as shown in fig. 3 (a). And then, carrying out photoelectric performance test on the device for researching the influence of plasma on the photoelectric performance of the device. In fact, direct CVD prepared 2D PdSe 2 has a large number of Se vacancy defects that can lead to significant fermi level pinning effects, which can limit the device in both response intensity and response speed, far below theoretical expectations.
The periodic photocurrent-time response curves of representative devices under different wavelengths of monochromatic light are shown in fig. 3 (b) - (c) before and after the O 2 plasma treatment. After the introduction of the O atoms, the conductive behavior of the carriers can be enhanced by capturing the potential. As is evident from a comparison of the two figures, pdSe 2 devices produced faster response and stronger photocurrents after O 2 plasma treatment, with lasers of 650nm (8.76 nW/μm 2)、532nm(2.25nW/μm2)、450nm(5.6nW/μm2) and 405nm (17.4 nW/μm 2). Further, I-V dependent properties of the treated devices were studied in FIG. 3 (d), which shows that the detector has a good response to voltage. The applicant then makes a simple calculation comparison of the performances of the device before and after the treatment under the irradiation of monochromatic light at different power densities, according to the calculation formula:
Iph=Ilight-Idark
Wherein I ph is a photocurrent generated when a voltage is applied, I light is a current when light is applied, I dark is a current when no light is applied, R is responsivity, P is power intensity of laser light irradiated on a channel, D is a photoelectric detection rate, a is a channel area of a device, and e is electric quantity of electrons.
As shown in (e) - (f) of fig. 3, after O 2 plasma treatment, the surface structure is changed, and the surface defects are increased, so that the life of the photo-generated carrier is shortened, and the response speed is increased; response time was increased from initial rise/off=3.12 s/2.89s to rise/off=0.10 s/0.26s. In addition, the device has good linear response capability to lasers with different wavelengths. In fig. 3 (g) - (h), after O 2 plasma treatment, the overall photoelectric properties of PdSe 2 are enhanced, both the responsivity and the detection rate are improved by more than 10 2 times, under the irradiation of laser with wavelength of 650nm and power density of 0.15nW/μm 2, The photoresponsivity is improved from 0.12A/W to 43.18A/W; The detection rate is increased from 2.63×10 8 Jones to 5.10×10 11 Jones. In addition, excellent response ability was exhibited at four different wavelengths of laser light of 650nm (8.76 nW/. Mu.m 2)、532nm(2.25nW/μm2)、450nm(5.6nW/μm2) and 405nm (17.4 nW/. Mu.m 2), FIG. 8. The O 2 plasma treatment leads to greater activity of the material, so that electron-hole pairs are generated and recombined more rapidly; in addition, according to the calculation result of DFT, the lattice doping of O can introduce sub-energy levels in the energy band, so that the response capability to light with different wavelengths is improved, and the spectral response range can be widened. And, in fig. 3 (i) - (l), the photoelectric performance of PdSe 2 -based photodetectors after treatment with O 2 plasma is more competitive than other photodetectors.
For further analysis of experimental results, the applicant calculated the energy band of PdSe 2 after O 2 plasma treatment by using DFT, see fig. 4. The orbital of O appears in the DOS plot of PdSe 2, indicating that O atoms can be doped into the lattice. The fermi level is defined at the 0eV position, and then the position of the fermi level in the forbidden band in fig. 4 also demonstrates the effect of p-type doping. And with the incorporation of O atoms, impurity levels are generated near the conduction band, so that the response spectrum range is widened.
FIG. 5 shows the periodic I-t response of the device before and after O 2 plasma treatment; (a) Intrinsic PdSe 2(b)O2 plasma treated PdSe 2. It is shown that O 2 plasma treatment effectively improves the performance of the PdSe 2 photodetector.
Conclusion(s)
O 2 plasma as a simple material treatment means, in the present application, the applicant used O 2 plasma for realizing O atom doping of PdSe 2. In this manner, crystal lattice vacancy filling of PdSe 2 and substitution of Se elements can be effectively achieved. The performance of the PdSe 2 photodetector can be effectively improved by controlling the treatment time of the O 2 plasma. Meanwhile, the doping of O atoms and passivation effect on the surface of the PdSe 2 realize controllable conversion of the performance of the PdSe 2 FET. The strategy for carrying out defect engineering regulation and control on the two-dimensional material through the O 2 plasma has a very good research prospect. The applicant can realize diversified doping and modification of materials by simply improving and developing the modes of plasma types, treatment process and the like, so that the method has universal application value and is beneficial to expanding the design path of the thin film optoelectronic device.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the oxygen doped palladium diselenide material is characterized by comprising the following specific steps:
(1) Firstly, evaporating Pd on an inverted Si/SiO 2 substrate by an electron beam evaporation coating instrument in a vacuum cavity in a heating evaporation mode by using an electron beam to obtain a palladium film;
(2) Then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film;
(3) Finally, O 2 plasma treatment is carried out on the palladium diselenide film, and the oxygen doped palladium diselenide material is obtained;
In the step (1), a sensor is arranged in the vacuum cavity and used for controlling the thickness of the vapor deposition palladium to be 3nm;
In the step (2), the chemical vapor deposition process conditions are as follows: using a chemical vapor deposition apparatus, a volume flow ratio of 9:1, the interior of the equipment is divided into a first area, a second area and a third area, the set growth temperature is 400 ℃, 600 ℃, the set heating time of the first area is 20 minutes, the set heating time of the second area and the third area is 10 minutes, the first area is heated for 10 minutes, at the moment, the second area and the third area start to be heated, so that the first area, the second area and the third area simultaneously reach the corresponding set growth temperature, and then the first area, the second area and the third area are insulated for 10 minutes;
In the step (3), the process conditions of the O 2 plasma treatment are as follows: the pressure was 0.3mbar and the treatment time was 30 minutes.
2. An oxygen-doped palladium diselenide material, characterized in that it is obtained by the preparation method according to claim 1.
3. The use of an oxygen-doped palladium diselenide material as claimed in claim 2 for the preparation of a photodetector.
4. The use according to claim 3, wherein the arrayed device is constructed by evaporating gold/titanium electrodes on the surface of the oxygen doped palladium diselenide material by a mask method.
5. The use according to claim 4, wherein the gold/titanium electrode has a thickness of 50nm.
6. The method according to claim 4, wherein the gold/titanium electrode has a channel spacing of 50 μm and an electrode size of 3mm by 3mm.
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