CN112909189B - Ternary transition metal nitride with adjustable high work function, preparation method and application thereof - Google Patents
Ternary transition metal nitride with adjustable high work function, preparation method and application thereof Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 51
- -1 transition metal nitride Chemical class 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 229920000144 PEDOT:PSS Polymers 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 37
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 15
- 229910002704 AlGaN Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 238000005289 physical deposition Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 238000004549 pulsed laser deposition Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000002310 reflectometry Methods 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 229910002601 GaN Inorganic materials 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000005533 two-dimensional electron gas Effects 0.000 description 1
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
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Abstract
The invention discloses a ternary transition metal nitride with an adjustable high work function, a preparation method and application thereof. The ternary transition metal nitride is Mo xM1‑x N, wherein M comprises any one of Ti, hf, zr, W, and x is more than or equal to 0.7 and less than or equal to 1. The ternary transition metal nitride provided by the invention has the advantages of controllable work function, high reflectivity, high conductivity and the like, and the film prepared by the ternary transition metal nitride can be applied to the fields of preparing top-emission OLED devices, si/PEDOT: PSS hybrid solar cells, high work function p-type organic semiconductors or inorganic semiconductors and the like.
Description
Technical Field
The invention belongs to the technical field of material growth, and particularly relates to a ternary transition metal nitride with an adjustable high work function, a preparation method and application thereof.
Background
Transition metal nitrides with high work functions and good conductivity can be used as energy level matching contact layers for many devices, such as anode structures in contact with hole injection layer materials in silicon-based OLED display devices, energy level matching layers between silicon and PEDOT PSS in Si/PEDOT: PSS hybrid solar cells, ohmic contacts for p-GaN or p-AlGaN with high work functions, heterojunction photovoltaic devices formed with high work function materials, and the like.
The silicon-based OLED display device combines the advantages of active light emission of an organic light-emitting diode display and the mature CMOS process technology. OLEDs are a popular research in the display field in recent years because they have advantages of fast reaction speed, low operating voltage, high contrast ratio, and capability of being manufactured into large-sized and flexible panels. In recent years, OLEDs have been widely used in display panels of mobile phones (small screen) and televisions (large screen), wherein the mobile phone display in the market in the middle of 2016 uses OLEDs up to 9900 tens of thousands, and 77 inch large screen OLED televisions have also been marketed, indicating that the OLED display era is truly coming. A common OLED device is bottom-emitting, but in active display, the OLED light emitting device is controlled by a Thin Film Transistor (TFT), so if the device emits light in the form of bottom emission, the light is blocked by the TFT and metal lines on the substrate as it passes through the substrate, thereby affecting the actual light emitting area. If the light is emitted from the upper part of the device, the circuit design of the substrate does not influence the light emitting area of the device. The OLED has lower working voltage under the same brightness, and can obtain longer service life. Therefore, the top-emitting device is the first choice for active display of small screens such as mobile phones and the like. The silicon-based OLED display device is just a top-emitting device. The structure of the top-emitting OLED device is: transparent or semitransparent cathode/electron injection layer/electron transport layer/organic light emitting layer/hole transport layer/hole injection layer/reflective anode. In a top-emitting device, the reflective anode is adjacent to the hole injection layer, and the magnitude of the difference between the HOMO level of the hole injection layer and the work function of the anode can affect the turn-on voltage and overall power consumption of the device. The work function of the anode needs to be equal to or higher than the HOMO level of the hole injection layer. Because the HOMO energy level of the organic hole injection layer material commonly used at present is more than 5.0eV, the work function of the anode structure of the silicon-based OLED micro-display device needs to be more than or equal to 5.0eV. In addition to matching work function to hole injection layer energy level, the anode electrode of top emission OLED device has the following requirements: 1. has high reflectivity (70%); 2. high conductivity (low resistivity and high mobility).
In the Si/PEDOT/PSS hybrid solar cell, the PEDOT/PSS forms a Schottky junction with n-type silicon to provide a built-in electric field for separating electrons and holes, and the photo-generated electrons and holes flow to a cathode and an anode respectively through an external circuit to form current. In order to increase the efficiency of the device, this can be done by enhancing light absorption, creating as many electron holes as possible, and improving charge transport. When electrons and holes are respectively transmitted to the corresponding electrodes, some electrons and holes are inevitably recombined, and the recombination of charges is reduced as much as possible, so that the efficiency of the device is effectively improved. In order to reduce charge recombination, a layer of thin layer with high work function can be inserted between Si and PEDOT: PSS, so that heterojunction formed by the thin layer with high work function and n-type silicon can improve built-in potential, electrons are effectively prevented from moving to an anode, charge recombination is effectively reduced, and efficiency of a device is improved. Since PEDPT PSS has a work function between 4.8 and 5.0eV, a thin layer with a work function greater than 5.0eV is selected as the energy level matching layer.
The GaN-based material is one of the novel wide-bandgap semiconductor materials of the third generation after materials such as first generation silicon (Si), germanium (Ge), second generation gallium arsenide (GaAs), indium phosphide (InP) and the like, has the characteristics of direct bandgap, large bandgap, high critical field strength, high heat conductivity, high carrier saturation velocity, high heterojunction interface two-dimensional electron gas concentration and the like, and has great application prospect in the fields of photoelectrons and microelectronics. For example, in the field of photoelectrons, gaN-based LEDs are used in backlight sources of liquid crystal televisions, computers, smart phones and the like, street lamps, landscape lighting, disinfection, sterilization and the like; in the field of microelectronics, gallium nitride-based high-temperature high-power electronic devices are widely applied to hybrid locomotives/electric automobiles, switching power supplies, oil exploitation, space exploration, rail transit, smart grids, mobile communication base stations and the like. In order to synchronize with the development of GaN epitaxial growth technology, to improve the performance of GaN-based devices, the contact resistivity of their ohmic contacts should be reduced, improving the reproducibility, durability, high temperature operability and mechanical integrity of the contacts. It has been a challenge to obtain low resistance, high thermal stability ohmic contacts to p-type gallium nitride (p-GaN) or p-AlGaN. One of the reasons for this is the lack of a suitable contact metal: according to the gold-semiconductor contact barrier model, ohmic contact can be realized only when the work function of a metal is larger than that of a p-type semiconductor without considering the surface state, and the work function of p-GaN or p-AlGaN is higher than 7.0eV, and the Pt with the highest work function in the metal is 5.65eV; secondly, highly doped p-GaN or p-AlGaN with hole carrier concentration higher than 10 18cm-3 is difficult to obtain; and thirdly, the surface of p-GaN or p-AlGaN has chemical activity, oxygen atoms are easy to adsorb, an intrinsic oxide layer is formed on the surface, and the oxide layer increases extra barrier height, prevents carrier transport from metal to semiconductor, and increases ohmic contact resistivity. Therefore, the key to obtain low-resistance p-GaN or p-AlGaN ohmic contact is to prepare a material with high work function and good conductivity, which has been a problem that has been desired to be solved in the industry.
And the transition metal nitride has the advantages of high work function, good conductivity, silicon-based process compatibility and the like, and meets the requirements of the device on the energy level matching layer.
Disclosure of Invention
The invention mainly aims to provide a ternary transition metal nitride with an adjustable high work function, a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
The embodiment of the invention provides a ternary transition metal nitride with an adjustable high work function, which is Mo xM1-x N, wherein M comprises any one of Ti, hf, zr, W, and x is more than or equal to 0.7 and less than or equal to 1.
Further, the work function of the ternary transition metal nitride is 5.0eV or more, wherein the work function of the ternary transition metal nitride increases with increasing metal Mo content.
The embodiment of the invention also provides a preparation method of the ternary transition metal nitride film with the adjustable high work function, which comprises the following steps: and using Mo xM1-x N or Mo xM1-x target material, wherein M comprises any one of Ti, hf, zr, W, x is more than or equal to 0.7 and less than or equal to 1, and forming a ternary transition metal nitride film on the substrate in a physical deposition mode.
The embodiment of the invention also provides a ternary transition metal nitride film with an adjustable high work function, which consists of Mo xM1-x N, wherein M comprises any one of Ti, hf, zr, W, and x is more than or equal to 0.7 and less than or equal to 1.
The embodiment of the invention also provides application of the ternary transition metal nitride or the ternary transition metal nitride film in preparing an energy level matching contact layer of a device.
Compared with the prior art, the high-work-function-adjustable ternary transition metal nitride film has the characteristics of high work function, high reflectivity and high conductivity, can be applied to an anode electrode of a top-emission type OLED device, so that the working voltage of the top-emission type OLED device is lower, the service life is longer, and the high-work-function-adjustable ternary transition metal nitride film can also be applied to a silicon/PEDOT: PSS hybrid solar cell, an ohmic contact of p-GaN or p-AlGaN with a high work function, a heterojunction photoelectric device formed by a high work function material, a photovoltaic device and the like.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a graph showing the results of the up test for the MoN film of example 1 of the present invention;
FIG. 2 is a graph showing the reflectance test results of the MoN film in example 1 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long-term research and a great deal of practice, and has proposed the technical scheme of the present invention, mainly by preparing a ternary transition metal nitride Mo xM1-x N film with a high work function, and simultaneously by controlling the content of metal Mo in the nitride, the present invention can reach the control of the work function, and can meet the requirements of anode electrode of a top-emitting OLED device and the requirements of silicon/PEDOT: PSS hybrid solar cell, ohmic contact of p-GaN or p-AlGaN with a high work function, and heterojunction photoelectric and photovoltaic devices formed by materials with a high work function.
One aspect of the embodiment of the invention provides a ternary transition metal nitride with an adjustable high work function, which is Mo xM1-x N, wherein M comprises any one of Ti, hf, zr, W, and x is more than or equal to 0.7 and less than or equal to 1.
Further, the work function of the ternary transition metal nitride is 5.0eV or more, wherein the work function of the transition metal nitride increases with the increase of the metal Mo content in the nitride.
Another aspect of the embodiments of the present invention provides a method for preparing a ternary transition metal nitride film with an adjustable high work function, which includes: and using Mo xM1-x N or Mo xM1-x target material, wherein M comprises any one of Ti, hf, zr, W, x is more than or equal to 0.7 and less than or equal to 1, and forming a ternary transition metal nitride film on the substrate in a physical deposition mode.
Further, the physical deposition mode comprises a pulse laser deposition mode or a magnetron sputtering mode.
Further, before depositing the ternary transition metal nitride, sequentially carrying out ultrasonic cleaning treatment on the silicon substrate by using acetone, ethanol and deionized water.
In some more specific embodiments, the process conditions used for the pulsed laser deposition method include: the temperature of the substrate is 100-500 ℃, the growth atmosphere is nitrogen atmosphere and the pressure is 0.5-3 Pa, the used laser is an excimer laser, the laser energy is 250-500mJ, and the laser frequency is 1-5Hz.
The excimer laser includes any one of KrF excimer laser, xeF excimer laser, arF excimer laser, xeCl excimer laser, F2 excimer laser, and is not limited thereto.
Wherein the KrF excimer laser has a wavelength of 248nm, the XeF excimer laser has a wavelength of 351-353nm, the ArF excimer laser has a wavelength of 193nm, the XeCl excimer laser has a wavelength of 308nm, and the F2 excimer laser has a wavelength of 157nm.
And further, annealing the ternary transition metal nitride film formed by a pulse laser deposition mode, wherein the annealing temperature of the annealing treatment is 100-500 ℃, the annealing atmosphere is nitrogen atmosphere and the pressure is 0.5-3 Pa, and the annealing time is 1-2 h.
In some more specific embodiments, the process conditions used in the magnetron sputtering deposition method include: the atmosphere is a mixed atmosphere of argon and nitrogen at room temperature, the pressure is 1-5 mttor, and the power is 200-400W.
Further, the flow ratio of the argon to the nitrogen is 3 to 5:1, preferably 3:1, 4:1 or 5:1.
Further, the thickness of the ternary transition metal nitride film is 50-100 nm.
Further, the substrate includes any one of glass and silicon, and is not limited thereto.
Further, the substrate includes a p-type semiconductor, and is not limited thereto.
Still further, the substrate includes p-GaN and/or p-AlGaN, and is not limited thereto.
In another aspect, the embodiment of the invention also provides a ternary transition metal nitride film with an adjustable high work function, which consists of Mo xM1-x N, wherein M comprises any one of Ti, hf, zr, W, and x is more than or equal to 0.7 and less than or equal to 1.
Further, the thickness of the ternary transition metal nitride film is 50-100 nm.
Another aspect of an embodiment of the present invention also provides the use of the foregoing ternary transition metal nitride or the foregoing ternary transition metal nitride film in the preparation of a device energy level matching contact layer.
Further the energy level matching contact layer comprises an anode structure of a silicon-based top-emission type OLED, and the Si/PEDOT is PSS hybridized solar cell.
Further, the energy level matching contact layer further comprises a p-type organic semiconductor or an inorganic semiconductor with a high work function forming ohmic contact with the ohmic contact layer.
Further, the ohmic contact layer comprises the ternary transition metal nitride or the ternary transition metal nitride film.
Further, the high work function p-type organic semiconductor or inorganic semiconductor and ohmic contact layer has a work function of 5 to 7.5eV.
The technical scheme of the invention is further described through the specific implementation and the attached drawings. Those skilled in the art will readily appreciate that the examples are presented solely to aid in the understanding of the invention and should not be construed as a specific limitation thereof.
The experimental materials used in the examples described below, unless otherwise specified, were all commercially available from conventional biochemicals.
Example 1: preparation of Mon film
The method comprises the steps of adopting a silicon substrate, sequentially carrying out ultrasonic cleaning on the silicon substrate for 5min by using acetone, ethanol and deionized water, drying the silicon substrate by using N 2, putting the silicon substrate into a magnetron sputtering deposition film system, setting a target material to be a Mo target, setting the air pressure to be 3mttor at room temperature, setting the working atmosphere to be a mixed atmosphere of Ar and N 2, setting the Ar and N 2 to be 4:1, setting the power to be 300W, setting the deposition time to be 35s, and obtaining a MoN film (FIG. 1 is a result graph of a work function characterization by UPS test of the MoN film in the embodiment, and FIG. 2 is a reflectivity test result graph of MoN).
By characterization, the work function of the MoN film is 6.14eV, the resistivity is 9.522 X10 -4 ohm cm, and the reflectivity of the 500-800nm wave band is higher than 75%.
Example 2: preparation of Mo 0.7Ti0.3 N film
And (3) adopting a glass substrate, sequentially carrying out ultrasonic cleaning on the glass substrate for 5min by using acetone, ethanol and deionized water, drying the glass substrate by using N 2, and putting the glass substrate into a magnetron sputtering deposition film system, wherein a target material is a Mo 0.7Ti0.3 target, the air pressure is 1mttor at room temperature, the working atmosphere is a mixed atmosphere of Ar and N 2, the Ar and N 2 are 3:1, the power is 200W, and the deposition time is 35s, so that the Mo 0.7Ti0.3 N film is obtained.
By characterization, the Mo 0.7Ti0.3 N film had a work function of 5.3eV.
Example 3: preparation of Mo 0.8Hf0.2 N film
And (3) carrying out ultrasonic cleaning on the p-GaN substrate for 5min sequentially by using acetone, ethanol and deionized water, drying the p-GaN substrate by using N 2, and putting the p-GaN substrate into a magnetron sputtering deposition film system, wherein a target material is a Mo 0.8Hf0.2 N target, the air pressure is 5mttor at room temperature, the working atmosphere is a mixed atmosphere of Ar and N 2, the Ar and N 2 are 5:1, the power is 400W, and the deposition time is 35s, so that the Mo 0.8Hf0.2 N film is obtained.
By characterization, the Mo 0.8Hf0.2 N film had a work function of 5.5eV.
Example 4: preparation of Mo 0.8Hf0.2 N film
The p-GaN substrate is adopted, acetone, ethanol and deionized water are sequentially used for carrying out ultrasonic cleaning for 5min, then N 2 is used for drying the p-GaN substrate, the p-GaN substrate is placed into a pulse laser deposition film system, a target material is set to be a Mo 0.8Hf0.2 N target, the temperature is 500 ℃, the working atmosphere is nitrogen atmosphere and the pressure is 3Pa, the used laser is a KrF excimer laser, the wavelength is 248nm, the laser energy is 500mJ, the laser frequency is 5Hz, the deposition time is 2h, and then annealing treatment is carried out, wherein the temperature and the air pressure are kept unchanged, and the annealing time is 2h, so that the Mo 0.8Hf0.2 N film is obtained.
By characterization, the Mo 0.8Hf0.2 N film had a work function of 5.5eV.
Example 5: preparation of Mo 0.9Zr0.1 N film
The method comprises the steps of adopting a silicon substrate, sequentially carrying out ultrasonic cleaning on the silicon substrate for 5min by using acetone, ethanol and deionized water, drying the silicon substrate by using N 2, putting the silicon substrate into a pulse laser deposition film system, setting a target material to be a Mo 0.9Zr0.1 N target, wherein the temperature is 100 ℃, the working atmosphere is nitrogen atmosphere and the pressure is 0.5Pa, adopting a XeF excimer laser with the wavelength of 351nm, the laser energy of 250mJ, the laser frequency of 1Hz, the deposition time of 2h, and then carrying out annealing treatment, wherein the temperature and the air pressure are kept unchanged, and the annealing time is 1.5h, thus obtaining the Mo 0.9Zr0.1 N film.
By characterization, the Mo 0.9Zr0.1 N film had a work function of 5.2eV.
Example 6: preparation of Mo 0.8W0.2 N film
The p-AlGaN substrate is adopted, acetone, ethanol and deionized water are sequentially used for carrying out ultrasonic cleaning on the p-AlGaN substrate for 5min, then N 2 is used for drying the p-AlGaN substrate and putting the p-AlGaN substrate into a pulse laser deposition film system, a target material is set to be a Mo 0.8W0.2 target, the temperature is 300 ℃, the working atmosphere is nitrogen atmosphere and the pressure is 1Pa, the used laser is a XeCl excimer laser, the wavelength is 308nm, the laser energy is 350mJ, the laser frequency is 3Hz, the deposition time is 2h, and then annealing treatment is carried out, wherein the temperature and the air pressure are kept unchanged, and the annealing time is 1h, so that the Mo 0.8W0.2 N film is obtained.
By characterization, the Mo 0.8W0.2 N film had a work function of 5.3eV.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the present invention.
Throughout this disclosure, where a composition is described as having, comprising, or including a particular component, or where a process is described as having, comprising, or including a particular process step, it is contemplated that the composition of the teachings of the present invention also consist essentially of, or consist of, the recited component, and that the process of the teachings of the present invention also consist essentially of, or consist of, the recited process step.
It should be understood that the order of steps or order in which a particular action is performed is not critical, as long as the present teachings remain operable. Furthermore, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (18)
1. The ternary transition metal nitride with the adjustable high work function is characterized in that the ternary transition metal nitride is Mo xM1-x N, wherein M comprises any one of Ti, hf, zr, W, x is more than or equal to 0.7 and less than or equal to 1, and the work function of the ternary transition metal nitride is more than or equal to 5.0eV.
2. The preparation method of the ternary transition metal nitride film with the adjustable high work function is characterized by comprising the following steps of: and forming a ternary transition metal nitride film on the substrate in a physical deposition mode by utilizing a Mo xM1-x N or Mo xM1-x target, wherein M comprises any one of Ti, hf, zr, W, x is more than or equal to 0.7 and less than or equal to 1, and the work function of the ternary transition metal nitride is more than or equal to 5.0eV.
3. The preparation method according to claim 2, characterized in that: the physical deposition mode comprises a pulse laser deposition mode or a magnetron sputtering deposition mode.
4. A method according to claim 3, wherein the process conditions used for pulsed laser deposition include: the temperature of the substrate is 100-500 ℃, the growth atmosphere is nitrogen atmosphere and the pressure is 0.5-3 Pa, the used laser is an excimer laser, the laser energy is 250-500mJ, and the laser frequency is 1-5Hz.
5. The method of manufacturing according to claim 4, wherein: the excimer laser comprises any one of a KrF excimer laser, a XeF excimer laser, an ArF excimer laser, a XeCl excimer laser and a F 2 excimer laser; wherein the KrF excimer laser has a wavelength of 248nm, the XeF excimer laser has a wavelength of 351-353nm, the ArF excimer laser has a wavelength of 193nm, the XeCl excimer laser has a wavelength of 308nm, and the F 2 excimer laser has a wavelength of 157nm.
6. The method according to claim 4 or 5, characterized by further comprising: and carrying out annealing treatment on the ternary transition metal nitride film formed in the pulse laser deposition mode, wherein the temperature of the annealing treatment is 100-500 ℃, the annealing atmosphere is nitrogen atmosphere and the air pressure is 0.5-3 Pa, and the annealing time is 1-2 h.
7. The method according to claim 3, wherein the process conditions adopted by the magnetron sputtering deposition method include: at room temperature, the atmosphere is a mixed atmosphere of argon and nitrogen, the pressure is 1-5 mittor, the power is 200-400W, and the flow ratio of the argon to the nitrogen is 3-5:1.
8. The preparation method according to claim 2, characterized in that: the thickness of the ternary transition metal nitride film is 50-100 nm.
9. The preparation method according to claim 2, characterized in that: the substrate comprises glass and/or silicon.
10. The preparation method according to claim 2, characterized in that: the substrate comprises a p-type semiconductor.
11. The method of manufacturing according to claim 10, wherein: the substrate includes p-GaN and/or p-AlGaN.
12. A high work function adjustable ternary transition metal nitride film is characterized in that: the film is composed of Mo xM1-x N, wherein M comprises any one of Ti, hf, zr, W, x is more than or equal to 0.7 and less than or equal to 1, and the work function of the ternary transition metal nitride is more than or equal to 5.0eV.
13. The ternary transition metal nitride film of claim 12, wherein: the thickness of the ternary transition metal nitride film is 50-100 nm.
14. Use of a ternary transition metal nitride according to claim 1 or a ternary transition metal nitride film according to any one of claims 12-13 for the preparation of a device energy level matching contact layer.
15. Use according to claim 14, characterized in that: the energy level matching contact layer comprises an anode structure of a silicon-based top-emission type OLED or a Si/PEDOT: PSS hybrid solar cell.
16. Use according to claim 14, characterized in that: the energy level matching contact layer further comprises a p-type organic semiconductor or an inorganic semiconductor with a high work function forming ohmic contact with the ohmic contact layer.
17. Use according to claim 16, characterized in that: the ohmic contact layer comprises the ternary transition metal nitride of claim 1 or the ternary transition metal nitride film of any one of claims 12-13.
18. Use according to claim 16, characterized in that: the work function of the p-type organic semiconductor or inorganic semiconductor with high work function and the ohmic contact layer is 5-7.5 eV.
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