CN117613140A - 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 120
- 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 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009832 plasma treatment Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000010894 electron beam technology Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 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
- 230000008569 process Effects 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 12
- 238000012546 transfer Methods 0.000 abstract description 12
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 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
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- 238000011161 development Methods 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 1
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- H01L31/18—
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- H01L31/0321—
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- H01L31/09—
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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, pd is evaporated to Si/SiO upside down by an electron beam evaporation coating instrument in a vacuum cavity by utilizing an electron beam heating evaporation mode 2 Obtaining a palladium film on a substrate; then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film; finally O is carried out on the palladium diselenide film 2 And performing plasma treatment to obtain the oxygen doped palladium diselenide material. The invention is realized by O 2 plasma injection method for PdSe 2 O atom doping is carried out, thereby realizing the PdSe doping 2 Regulating and controlling performance; through regulating and controlling the doping amount of O, the method realizes the PdSe-based doping amount 2 Is generated by the transfer characteristic of the field effect transistorp-type transition and this variation 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 recognized as a direction of development in the miniaturization of optoelectronic devices. However, intrinsic TMDCs often suffer 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 few in TMDCs family, and has potential application potential of photoelectric devices. At present, the PdSe is grown by a chemical vapor deposition method, a magnetron sputtering method and the like from bottom to top 2 、PtS 2 Noble metal chalcogenides, and the like, can be manufactured at low cost to realize the application of photoelectric devices. 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, pd is evaporated to Si/SiO upside down by an electron beam evaporation coating instrument in a vacuum cavity by utilizing an electron beam heating evaporation mode 2 Obtaining a palladium film on a substrate;
(2) Then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film;
(3) Finally O is carried out on the palladium diselenide film 2 And performing plasma treatment 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 step (3), O 2 The technological conditions of the plasma treatment are as follows: the treatment time was 30 minutes using a DieneATTO plasma cleaner, germany, 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 to Si/SiO upside down by an electron beam evaporation coating instrument in a vacuum environment of a vacuum cavity by utilizing an electron beam heating evaporation mode 2 The thickness (3 nm) of the evaporated Pd is controlled by a sensor in a vacuum cavity on a substrate, and then the selenization reaction is carried out on a Pd film by a chemical vapor deposition method to obtain the PdSe with large area uniformity 2 Film, finally, go through O 2 And (3) carrying out plasma treatment to modify the palladium diselenide, and then evaporating 50nm Au electrodes on the palladium diselenide by a mask method in 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 palladium diselenide obtained by this method, further through O 2 Modification of palladium diselenide by key operations of plasma treatmentSex, by comparison with O 2 And controlling plasma treatment parameters, filling palladium diselenide vacancies grown by chemical vapor deposition by utilizing oxygen, and regulating and controlling carriers. Compared with other methods such as ozone treatment, the method has higher controllability and lower cost.
The invention is realized by O 2 plasma injection method for PdSe 2 O atom doping is carried out, thereby realizing the PdSe doping 2 Regulating and controlling performance; through regulating and controlling the doping amount of O, the method realizes the PdSe-based doping amount 2 The transfer characteristics of the field effect transistor of (c) are p-type converted, and the conversion has stability.
The invention is implemented by the method of the invention 2 Control of plasma treatment duration, using O to realize PdSe for chemical vapor deposition growth 2 And filling gaps, so as to realize the regulation and control of carriers. Through O 2 After plasma treatment, based on PdSe 2 The photoelectric response capability of the device comprises responsivity and detection rate which are improved by hundreds of times, and the response time is also effectively accelerated. In addition, by the method of O 2 The control of the plasma treatment duration can controllably change the carrier transfer characteristics of the transistor. First, through O 2 The plasma can realize the effect of PdSe 2 The Se vacancy in the semiconductor device is subjected to lattice doping of O atoms, 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. This work is done by O 2 The modification of the two-dimensional material photoelectric device is realized in a plasma mode, so that the method can be easily expanded to other two-dimensional devices, has the value of universality application, and provides a thinking 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 invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is O 2 PdSe before and after plasma treatment 2 Characterization. (a) PdSe 2 A schematic top view and a schematic front view of a folded pentagonal fold structure. (b) schematic illustration of Pd principle of electron beam evaporation. (c) Chemical vapor deposition growth of PdSe 2 Schematic diagram. (d) Through O 2 plasma treated PdSe 2 Schematic device diagram. (e) For PdSe 2 AFM characterization of thickness. (f) Different time lengths O 2 plasma treatment of PdSe 2 Is described. (g) - (i) O 2 PdSe before and after plasma treatment 2 The XPS energy spectrum of (g) Pd 3d (h) Se 3d and (i) O1 s.
FIG. 2 is O 2 PdSe before and after plasma treatment 2 Electrical performance of field effect transistors. (a) O (O) 2 plasma treated PdSe 2 FET device schematic; (b) O (O) 2 PdSe before and after plasma treatment 2 Is a transfer characteristic of (2); (c) PdSe with p-type transfer characteristic 2 A device; (d) O (O) 2 plasma treatment to produce O doped PdSe 2 Structural changes in (2); (e) Intrinsic PdSe 2 Device and (f) O 2 An output characteristic curve after plasma processing; (g) 0min, (h) 10min and (i) 30min O 2 plasma treated PdSe 2 Transfer characteristics at different leakage voltages.
FIG. 3 is O 2 Plasma treated PdSe 2 And intrinsic PdSe 2 And comparing photoelectric performances of the photoelectric devices. (a) PdSe 2 Schematic device structure. (b) O (O) 2 Plasma treatment of PdSe 2 Device and (c) intrinsic PdSe 2 The device responds to periodic photoelectricity of lasers with different wavelengths. (d) O (O) 2 Plasma treatment of PdSe 2 The change relation of the photocurrent of the device with the voltage. (e) PdSe 2 Response time profile of the device. Rise/down=3.124 s/2.888s. (f) O (O) 2 Plasma treatment of PdSe 2 Device response time. rise/down=0.100 s/0.235s. O (O) 2 The responsivity (g) before and after plasma treatment is compared with the detection rate (h). (i) O (O) 2 Plasma treatment of PdSe 2 I-V curve (j-k) O under different wavelength lasers and darkness of device 2 plasma treated PdSe 2 The device was compared to the responsivity and detection rate of the work in the literature. (l) O (O) 2 Plasma treatment of PdSe 2 Photocurrent of the device under laser with different wavelengths. The laser is 650nm (8.76 nW/. Mu.m) 2 )、532nm(2.25nW/μm 2 )、450nm(5.6nW/μm 2 ) And 405nm (17.4 nW/. Mu.m) 2 )。
FIG. 4 is a graph of the relationship of O 2 PdSe after plasma treatment 2 DFT computation of (2); (a) an energy band structure; (b) DOS; (c) work function.
FIG. 5 is O 2 periodic I-t responses of the device before and after plasma treatment; (a) Intrinsic PdSe 2 (b)O 2 PdSe after plasma treatment 2 。
FIG. 6 is a graph of different durations O 2 plasma treatment of PdSe 2 Is characterized by an optical microscope; (a) 0min (b) 10min (c) 30min and (d) 60min, magnification of 50×.
FIG. 7 is a graph of different durations O 2 plasma treated PdSe 2 AFM characterization of (a); (a) 0min (b) 10min (c) 30min (d) 60min.
FIG. 8 is O 2 PdSe after plasma treatment 2 The responsivity and the detection rate of the device under four wavelength lasers are in a relation of change along with the 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, pd is evaporated to Si/SiO upside down by an electron beam evaporation coating instrument in a vacuum cavity by utilizing an electron beam heating evaporation mode 2 Obtaining a palladium film on a substrate;
(2) Then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film;
(3) O is carried out on the palladium diselenide film 2 performing plasma treatment 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 step (3), O 2 The technological conditions of the plasma treatment are as follows: the treatment time was 30 minutes using a DieneATTO plasma cleaner, germany, 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) is shown PdSe 2 As can be seen from the front view and the top view, the structure of PdSe 2 Having a unique folded pentagonal structure which allows PdSe to be formed 2 There is an in-plane anisotropy characteristic. This anisotropic lattice structure allows PdSe to 2 Exhibiting more interesting photovoltaic anisotropy. In FIG. 1, (b) and (c) are PdSe 2 A method for preparing a film. Initially, pd is evaporated to Si/SiO upside down by an electron beam evaporation coating apparatus under a near vacuum environment by using an electron beam heating evaporation mode 2 On the substrate, the thickness (3 nm) of the evaporated Pd is controlled by a sensor in a cavity, and then the selenization reaction is carried out on the Pd film by a chemical vapor deposition method to obtain the PdSe with large area uniformity 2 A film. Secondly, the material PdSe is prepared by electron beam evaporation 2 The 50nmAu/Ti electrode was vapor deposited by a mask method to form an arrayed device, and the prepared PdSe was subjected to AFM as shown in fig. 1 (d) 2 The film was characterized and in FIG. 1 (e), it can be seen that the PdSe produced 2 Has a thickness of 18.07nm and a relatively flat surface.
To illustrate O 2 The plasma treatment results in PdSe 2 The changes that occur are raman characterized. In FIG. 1 (f) there are shown different durations O 2 plasma treated PdSe 2 Is a raman spectrum of (c). As the treatment duration varies, the raman characteristic peak also varies significantly. After a long treatment, 890cm of the product were observed in sequence -1 (Se＝O)、830cm -1 (Se-O 2 ) And 630cm -1 Peak position at (pd=o).
Next, applicants utilized XPS for O 2 PdSe before and after plasma treatment 2 The elemental composition was characterized and the fitting results are shown in fig. 1 (g) - (i). Intrinsic PdSe 2 The 3d peak of Pd in the middle contains two, including 3d at 337.1eV 5/2 And 3d at 342.5eV 3/2 And go through 30min O 2 plasma treatment, energy reduction of Pd 3d peak position close to 1.0eV, 3d 5/2 And 3d 3/2 The peaks shifted to 336.2eV and 341.3eV, respectively, in addition to this, the Pd 3d spin-orbit splitting peak broadened, mainly due to O 2 Metastable PdO at 343.2eV and 338.2eV after plasma treatment 2 (Pd 4+ ) The peak was enhanced and typical PdO (Pd) was produced at 337.0eV, 342.2eV 2+ ) A peak; it is evident that a distinct characteristic peak appears at 59.3eV, a phenomenon derived from SeO 2 In addition to the increase in Se 3d peak position, the energy becomes low due to the shift of 0.2 eV. In addition, O produced a peak at 531.2eV, while the 532.7eV peak shifted to 533.0eV. XPS results indicate that O is successfully doped into the lattice, forming pd=o bonds.
Next, the applicants have prepared an O-based 2 plasma treated PdSe 2 Transistor array with intrinsic PdSe 2 Transistor performance comparisons were made. The correlation results are shown in fig. 2.
In FIG. 2, (a) shows a schematic structure of the device by the method shown in PdSe 2 Depositing Au/Ti with the thickness of 50nm on the surface to form a source electrode and a drain electrode, thereby realizing the alignment ofTesting of device performance.
Transfer characteristic analysis for device, as in FIG. 2 (b), 30min O 2 plasma treatment to make intrinsic PdSe 2 The bipolar transfer behavior becomes the p-type transfer mechanism (fig. 2 (c)), and the on/off current ratio is changed from the first 10 3 Lifted to 10 6 This is consistent with the XPS test results described above, indicating that the O atoms were successfully filled into crystal lattice Se vacancies (FIG. 2 (d)). 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.
O is shown in FIGS. 2 (e) - (f) 2 I of device before and after plasma treatment ds -V ds Linear relationship, ability of drain voltage device to continuously regulate channel conductance and output characteristics after processing relative to intrinsic PdSe 2 Significant changes occurred.
Further, by (g) - (i) in FIG. 2, O was 0min, 10min and 30min, respectively 2 Sensitivity of the device to bias voltage after plasma treatment varies with O 2 The device exhibited stronger p-type conduction behavior with increased plasma processing time. The result is probably due to Se vacancies along with O 2 The increase of the plasma treatment duration is gradually filled by O atoms; further illustrating the long-term O, in terms of roughness characterization changes exhibited by FIGS. 6 and 7 2 The plasma gradually passivates the surface, which effectively suppresses the tunneling current; in addition to O atom and O 2 Adsorption with unreacted Se and Pd on the surface to form amorphous compound, and then the amorphous compound is formed into PdSe 2 And a layer of oxide is applied to the surface, so that the performance stability of the device is improved.
Next, applicants have paid for O 2 PdSe before and after plasma treatment 2 An array device was prepared 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 There are a large number of Se vacancy defects which can lead to significant Fermi level pinning effects, making the device either loudBoth the stress intensity and the response speed are limited, which is far lower than the theoretical expectation.
O 2 The periodic photocurrent-time response curves of representative devices under different wavelengths of monochromatic light irradiation before and after plasma treatment are shown in fig. 3 (b) - (c). 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, the flow through O 2 After the plasma treatment, pdSe 2 The device can generate faster response speed and stronger photocurrent, and the laser is 650nm (8.76 nW/μm 2 )、532nm(2.25nW/μm 2 )、450nm(5.6nW/μm 2 ) And 405nm (17.4 nW/. Mu.m) 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:
I ph ＝I light -I dark
wherein I is ph I to photocurrent generated when voltage is applied light I is the current in the presence of illumination dark The current is the current when no light exists, R is the responsivity, P is the power intensity of laser irradiated on a channel, D is the photoelectric detection rate, A is the channel area of the device, and e is the electric quantity of electrons.
The results are shown in FIGS. 3 (e) - (f), O 2 After plasma treatment, the surface structure is changed, and the surface defects are increased, so that the service life of the photo-generated carriers is shortened, and the response speed is accelerated; 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 linearity for lasers with different wavelengthsResponse capability. In FIG. 3 (g) - (h), through O 2 After the plasma treatment, pdSe 2 The photoelectric performance of the system is enhanced integrally, and the response and the detection rate are improved by more than 10 2 The power density is 0.15nW/μm at a wavelength of 650nm 2 The light responsivity is improved from 0.12A/W to 43.18A/W under the irradiation of laser; the detection rate is 2.63 multiplied by 10 8 Jones is promoted to 5.10X10 11 Jones. In addition, at 650nm (8.76 nW/. Mu.m) 2 )、532nm(2.25nW/μm 2 )、450nm(5.6nW/μm 2 ) And 405nm (17.4 nW/. Mu.m) 2 ) Four different wavelengths of laser light all showed excellent response capability, fig. 8. Through O 2 The plasma treatment results in greater activity of the material, allowing more rapid generation and recombination of electron-hole pairs; 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), compared with other photodetectors, O is used 2 After the plasma treatment, based on PdSe 2 The photoelectric performance of the photoelectric detector has larger competitiveness.
For further analysis of experimental results, the applicant aimed at O by using DFT 2 PdSe after plasma treatment 2 The energy bands of (2) were calculated as shown in figure 4. At PdSe 2 The orbitals of O appear in DOS diagrams of (c), 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 O 2 periodic I-t responses of the device before and after plasma treatment; (a) Intrinsic PdSe 2 (b)O 2 PdSe after plasma treatment 2 . Description O 2 The plasma treatment effectively improves the PdSe 2 Performance of the photodetector.
Conclusion(s)
O 2 plasma is a simple material treatment means, in this application, applicants will have O 2 plasma for use inRealize the PdSe 2 O atoms of (a) are doped. In this way, the PdSe can be effectively realized 2 Is a crystal lattice vacancy filling and substitution of Se elements. By reacting O with 2 Control of plasma treatment time length can effectively improve PdSe 2 Performance of the photodetector. At the same time, doping of O atoms and doping of PdSe 2 Passivation effect of the surface to realize PdSe 2 The performance of the FET is controllably shifted. This is achieved by O 2 The strategy of performing defect engineering regulation and control on the two-dimensional material by plasma has 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 (9)
1. The preparation method of the oxygen doped palladium diselenide material is characterized by comprising the following specific steps:
(1) Firstly, pd is evaporated to Si/SiO upside down by an electron beam evaporation coating instrument in a vacuum cavity by utilizing an electron beam heating evaporation mode 2 Obtaining a palladium film on a substrate;
(2) Then carrying out selenizing reaction on the palladium film through chemical vapor deposition to obtain a palladium diselenide film;
(3) Finally O is carried out on the palladium diselenide film 2 And performing plasma treatment to obtain the oxygen doped palladium diselenide material.
2. The method according to claim 1, wherein in the step (1), a sensor for controlling the thickness of the vapor deposited palladium to 3nm is provided in the vacuum chamber.
3. The method according to claim 1, wherein 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.
4. The process according to claim 1, wherein in step (3), O 2 The technological conditions of the plasma treatment are as follows: the pressure was 0.3mbar and the treatment time was 30 minutes.
5. An oxygen-doped palladium diselenide material, characterized in that it is obtained by the preparation method according to any one of claims 1 to 4.
6. The use of an oxygen-doped palladium diselenide material as defined in claim 5 for the preparation of a photodetector.
7. The method according to claim 6, wherein the arrayed devices are constructed by evaporating gold/titanium electrodes on the surface of the oxygen-doped palladium diselenide material by a mask method.
8. The use according to claim 7, wherein the gold/titanium electrode has a thickness of 50nm.
9. The use according to claim 7, wherein the gold/titanium electrode has a channel spacing of 50 μm and electrode dimensions of 3mm x 3mm.
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| WO2014182697A1 (en) * | 2013-05-08 | 2014-11-13 | The University Of Houston System | Methods for the synthesis of arrays of thin crystal grains of layered semiconductors sns2 and sns at designed locations |
| CN113293395A (en) * | 2021-04-29 | 2021-08-24 | 齐齐哈尔大学 | Molybdenum selenide catalyst, preparation method thereof and application thereof in hydrogen evolution by electrolyzing water |
| CN114544024A (en) * | 2022-02-21 | 2022-05-27 | 电子科技大学 | Flexible thermosensitive sensor and preparation method thereof |
| CN115874151A (en) * | 2022-08-30 | 2023-03-31 | 湘潭大学 | Preparation method of large-area palladium sulfide or/and palladium disulfide nano film |
| CN116913762A (en) * | 2023-07-21 | 2023-10-20 | 济南大学 | Implementing PdSe based on Lewis acid concentration 2 P-type doping quantitative method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014182697A1 (en) * | 2013-05-08 | 2014-11-13 | The University Of Houston System | Methods for the synthesis of arrays of thin crystal grains of layered semiconductors sns2 and sns at designed locations |
| CN113293395A (en) * | 2021-04-29 | 2021-08-24 | 齐齐哈尔大学 | Molybdenum selenide catalyst, preparation method thereof and application thereof in hydrogen evolution by electrolyzing water |
| CN114544024A (en) * | 2022-02-21 | 2022-05-27 | 电子科技大学 | Flexible thermosensitive sensor and preparation method thereof |
| CN115874151A (en) * | 2022-08-30 | 2023-03-31 | 湘潭大学 | Preparation method of large-area palladium sulfide or/and palladium disulfide nano film |
| CN116913762A (en) * | 2023-07-21 | 2023-10-20 | 济南大学 | Implementing PdSe based on Lewis acid concentration 2 P-type doping quantitative method and application thereof |
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