CN113241294A - Preparation method of hollow diamond nanowire array group with low field emission opening threshold - Google Patents

Preparation method of hollow diamond nanowire array group with low field emission opening threshold Download PDF

Info

Publication number
CN113241294A
CN113241294A CN202110432576.5A CN202110432576A CN113241294A CN 113241294 A CN113241294 A CN 113241294A CN 202110432576 A CN202110432576 A CN 202110432576A CN 113241294 A CN113241294 A CN 113241294A
Authority
CN
China
Prior art keywords
diamond
boron
diamond film
array group
field emission
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110432576.5A
Other languages
Chinese (zh)
Inventor
郑宇亭
刘金龙
李成明
刘彦辉
魏俊俊
陈良贤
李文君
石志城
欧阳晓平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Shunde Graduate School of USTB
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Publication of CN113241294A publication Critical patent/CN113241294A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/022—Manufacture of electrodes or electrode systems of cold cathodes
    • H01J9/025—Manufacture of electrodes or electrode systems of cold cathodes of field emission cathodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H01J1/304—Field-emissive cathodes
    • H01J1/3042—Field-emissive cathodes microengineered, e.g. Spindt-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H01J1/308—Semiconductor cathodes, e.g. cathodes with PN junction layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/30—Cold cathodes
    • H01J2201/304—Field emission cathodes
    • H01J2201/30403—Field emission cathodes characterised by the emitter shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/30—Cold cathodes
    • H01J2201/304—Field emission cathodes
    • H01J2201/30446—Field emission cathodes characterised by the emitter material
    • H01J2201/30453—Carbon types
    • H01J2201/30457—Diamond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/30—Cold cathodes
    • H01J2201/308—Semiconductor cathodes, e.g. having PN junction layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2209/00—Apparatus and processes for manufacture of discharge tubes
    • H01J2209/02—Manufacture of cathodes
    • H01J2209/022—Cold cathodes
    • H01J2209/0223—Field emission cathodes

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cold Cathode And The Manufacture (AREA)

Abstract

The invention relates to a preparation method of a hollow diamond nanowire array group with a low field emission opening threshold, belonging to the field of semiconductor device preparation. The doping concentration is 1 x 1021cm‑3To 1X 1023cm‑3The boron-doped diamond is controlled by precision grinding and polishing to ensure that the surface roughness is in the range of 80-120 nm. Then the silicon wafer is co-bonded with the Si wafer in O2And Cl2And performing inductively coupled plasma reactive ion etching for 20-90min under the condition that the gas source ratio is 2: 1-10: 1. Then, the etched boron-doped diamond sheet is treated by hydrogen plasma for 5-30min under the conditions of 5-7kPa and the temperature of 600-800 ℃, thereby obtaining the ultra-low field emissionA high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with a firing voltage threshold is used for high-performance electron-emitting devices and the like.

Description

Preparation method of hollow diamond nanowire array group with low field emission opening threshold
Technical Field
The invention belongs to the field of semiconductor device preparation. Especially, the doping concentration is 1 × 1021cm-3To 1X 1023 cm-3The boron-doped diamond is controlled by precision grinding and polishing to ensure that the surface roughness is in the range of 80-120 nm. Then the silicon wafer is co-bonded with the Si wafer in O2And Cl2And performing inductively coupled plasma reactive ion etching for 20 to 90min under the condition that the gas source is 2:1 to 10: 1. And then, treating the etched boron-doped diamond sheet for 5-30min by hydrogen plasma under the conditions of 5-7kPa and the temperature of 600-800 ℃, thereby obtaining the high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with the ultra-low field emission starting voltage threshold value, which is used for high-performance electron emission devices and the like.
Background
The low-dimensional semiconductor field emission cathode has ideal application prospect in the aspects of flat panel displays, electron microscopes, vacuum microelectronic devices and the like. The field electron emission refers to a physical process that electrons in a solid penetrate through a surface potential barrier to enter vacuum through a tunnel effect, and is an important electrical property of a low-dimensional nano material, and the key of the application of a nano material field emission device is a high-performance field emission cathode material. An excellent field emission cathode material should have high conductivity and high aspect ratio channels to enhance the local electric field at the tip. Different material processing techniques have been developed to produce one-dimensional carbon-based nanostructures with high aspect ratios, such as amorphous carbon nanotips, Carbon Nanofibers (CNF), Carbon Nanotubes (CNF) and diamond nanotips or nanocones. Among them, the CNT has a low on-field value and a high field emission current density value, and has the best characteristics of a field emission cathode material. However, the CNT field emitter has problems of unstable emission current at high voltage, poor oxidation resistance and heat resistance, and difficulty in cathode assembly.
Diamond is a multifunctional material integrating a plurality of extreme physical and chemical properties, such as highest hardness and thermal conductivity, extremely high optical transmittance and refractive index, ultra-wide band gap, ultra-high breakdown electric field, high carrier mobility, low dielectric constant, negative electron affinity, chemical inertness and the like, and the field emission performance of the diamond can be comparable to that of a CNT field emitter. The low-dimensional nano material has higher length-diameter ratio and thinner tip, which is beneficial to obtaining higher field enhancement factor, thereby reducing the field emission starting field and enhancing the field emission current. The one-dimensional nanostructure of diamond is therefore considered an ideal field emission cathode material. In recent years, with the development of diamond surface processing technology, one-dimensional diamond nanomaterials exhibit excellent properties. The one-dimensional diamond nano material has the size of nanometer level, so the property of electrons can be adjusted by the low-dimensional effect, thereby changing the property of the material, and the one-dimensional diamond nano material not only has the inherent physicochemical property of a diamond film, but also has the unique property of some special structures. Such as super-elastic deformation at nanometer size, high specific surface area, tip effect, etc.
In order to improve the field emission performance of boron-doped diamond, boron-doped diamond nanowires with high aspect ratio need to be prepared. Boron-doped diamond has extremely high hardness and stable chemical properties, and a mask plate method is generally used for plasma etching at present to prepare a one-dimensional diamond nanowire array which is orderly arranged. However, the preparation method is complex and high in cost, and a subsequent mask plate removing process exists. The field emission performance of the material and the structure still needs to be further improved, and especially higher requirements are put forward on the material preparation and the structure design of diamond.
Disclosure of Invention
In order to fill the defects and realize the expectation of higher field emission performance, a preparation method of a high-density high-length-diameter-ratio hollow hydrogen terminal diamond nanowire array group with an ultralow field emission starting voltage threshold is provided according to the processing and etching characteristics of diamond. By setting the doping concentration to 1X 1021cm-3To 1X 1023cm-3The boron-doped diamond film is precisely ground and polished to control the surface roughness of the boron-doped diamond film within the range of 80-120 nm. Then the silicon wafer is co-bonded with the Si wafer in O2And Cl2And performing inductively coupled plasma reactive ion etching for 20 to 90min under the condition that the gas source is 2:1 to 10: 1. And then, treating the etched boron-doped diamond sheet for 5-30min by hydrogen plasma under the conditions of 5-7kPa and the temperature of 600-800 ℃, thereby obtaining the high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with the ultra-low field emission starting voltage threshold value, which is used for high-performance electron emission devices and the like.
The technical scheme of the invention is as follows:
a method for preparing hollow diamond nano-wire array group with low field emission opening threshold is characterized in that the doping concentration is 1 multiplied by 1021cm-3To 1X 1023cm-3Controlling the surface roughness of the boron-doped diamond within the range of 80-120nm through precise grinding and polishing; then the polished boron-doped diamond film and the Si wafer are put together in O2And Cl2Performing inductively coupled plasma reactive ion etching for 20 to 90min under the condition that the gas source ratio is 2:1 to 10: 1; then the etched boron-doped diamond sheet is treated by hydrogen plasma for 5-30min under the conditions of 5-7kPa and the temperature of 600-800 ℃,thereby obtaining the hollow hydrogen terminal diamond nanowire array group with high density and high length-diameter ratio and ultra-low field emission starting voltage threshold value, which is used for high-performance electron emission devices.
The preparation method of the hollow diamond nanowire array group with the low field emission opening threshold is characterized by comprising the following steps:
step 1: preparing a boron-doped diamond film:
depositing and preparing a boron-doped diamond film by adopting an MPCVD system;
step 2: precise grinding and polishing control of the boron-doped diamond film;
flattening the surface of the diamond film by adopting diamond grinding equipment, grinding the diamond film by using diamond powder with different particle sizes, and precisely polishing until the surface roughness is between 80 and 120 nm;
and step 3: cleaning the surface of the diamond film:
ultrasonically cleaning the surface of the grinded boron-doped diamond film to remove the residual diamond powder due to mechanical grinding; firstly, carrying out acid cleaning treatment on the cleaned boron-doped diamond film, and placing the diamond film in a sulfuric acid: heating a solution with the concentration of nitric acid of 5:1, boiling for 30-60min after the solution is boiled; then, ultrasonic cleaning is carried out on the diamond film by sequentially using acetone, alcohol and deionized water, the ultrasonic power is 50-300W, the cleaning is carried out for 25-35min each time, and the diamond film is dried; ultrasonically cleaning the diamond film for 2 times by using deionized water, wherein the ultrasonic power is 50-300W, cleaning is carried out for 25-35min each time, drying is carried out, and residual solution on the surface of the boron-doped diamond film is removed;
and 4, step 4: preparing diamond nanowires:
placing the boron-doped diamond film subjected to acid cleaning treatment and a Si wafer in an inductively coupled plasma reactive ion etching device together, and performing O-ion etching2And Cl2Carrying out maskless etching under the condition that the gas source is mixed in a ratio of 2:1 to 10:1 to prepare a diamond nanowire array group;
and 5: hydrogenation of diamond nanowires:
and (3) performing hydrogen plasma treatment on the boron-doped diamond nanowires by adopting an MPCVD device to realize surface hydrogen termination of the diamond nanowire array group.
Further, the preparation step of the boron-doped diamond film in the step 1 is to set the deposition temperature range to 740-970 ℃ and use CH4、H2As the reaction gas, trimethyl borate (B (OCH)3)3) As a boron source, H2The flow rate is 150-4Introducing H of boron source with the flow rate of 6-25sccm2The flow rate was 20 sccm.
Further, the precise grinding and polishing control of the boron-doped diamond film in the step 2 is as follows: in the surface flattening process, diamond powder with the grain diameters of 120 microns, 60 microns, 40 microns, 30 microns, 15 microns and 5 microns is adopted in sequence, the rotating speed of a grinding disc is 20-100rpm, the external load is 100-1000g, the diamond film is ground until the surface roughness is lower than 200nm, and then the diamond film is precisely polished by 5 microns, 3.5 microns and 1 micron until the surface roughness is 80-120 nm.
Further, the hollow diamond nanowire in the step 4 is prepared by adopting an inductively coupled plasma etching method and introducing reaction gas O2And Cl2The flow rates of the silicon nitride and the silicon nitride are respectively 30-80sccm and 3-40sccm (the mixing ratio of 2:1 to 10: 1), the pressure of the chamber is 1-9Pa, the ICP power is 200-700W, and the etching time is 30-180 min.
Further, the hydrogenation of the diamond nanowire in the step 5 is performed by using hydrogen plasma etching, wherein the etching is performed for 5-30min under the conditions that the flow of H2 is 200-; and cooling to room temperature in a hydrogen atmosphere after etching.
The key of the implementation process of the invention is as follows:
1) the surface roughness of the boron-doped diamond film needs to be kept in a certain range, and after etching, the surface of the excessively rough surface can be locally enhanced and unevenly caused by obvious fluctuation and unevenness, so that the etching surface roughness is further deteriorated instead of forming a uniform and dense nanowire group. Whereas etching of the diamond surface is relatively more uniform if the roughness is too low, resulting in inefficient nanowire structure formation and inadequate nanowire density. In the process of using grinding equipment to flatten the surface of the diamond film, diamond powder with different particle sizes is used for grinding the diamond film. The diamond film is ground until the surface roughness is lower than 200nm by using diamond powder with the grain diameters of 120 mu m, 60 mu m, 40 mu m, 30 mu m, 15 mu m and 5 mu m in sequence, the rotating speed of a grinding disc is 20-100rpm, and the external load is 100-1000 g. Then precisely polishing the materials by adopting 5 mu m, 3.5 mu m and 1 mu m in sequence until the surface roughness is between 80 and 120 nm.
2) The etching time of the boron doped diamond is also critical. The etching time is short, and the nanowire with high length-diameter ratio cannot be formed. And the diameter of the diamond nanowires should theoretically decrease gradually with time, whereas the diameter increases with the etching time in the case of the Si coupon. This indicates that the surface of the boron-doped diamond nanowires also undergoes a redeposition process during etching. Thus indicating that either too long or too short an etch time is not suitable.
3) A local electric field is created near the boron atoms on the diamond surface, which favors the preferential formation of nanowires at the beginning of etching. Under the condition of low or medium boron-doped concentration, the diamond nanowires are distributed unevenly and sparsely, and under the condition of high boron-doped concentration, the diamond nanowires are distributed relatively evenly and have high density. The density of nanowires increases with increasing boron doping concentration. The doping concentration of boron can greatly affect the density of nanowire formation, mainly the local enhancement of the electric field (which emits a greater number of electrons) near the boron doping atoms causes the area around the boron sites to preferentially etch during etching.
4) And carrying out maskless etching together with the Si wafer under the condition of mixed gas of oxygen and chlorine. The annular Si oxide formed on the surface of the nano-needle at the initial stage of forming the nano-needle plays the role of a micro-mask. Simultaneous gas source O2And Cl2The ratio of (A) to (B) is kept at 2:1 to 10: 1. Too low Cl2The addition amount does not play a role in promoting the formation of diamond nanowires and influences sp3Graphitization transformation of the phase. And too high Cl2Will react with sp2Phase formation bonding to form chlorides affecting diamond sp3Oxidation of the phase thereby affecting the sodiumAnd (5) forming rice noodles.
Compared with the prior art, the invention has the beneficial effects that:
1) the emission starting electric field (E) of the high-density hollow hydrogen terminal diamond nanowire array group with high length-diameter ratioTOWhen the current density reaches 10 muA/cm2Corresponding applied electric field) and threshold field (E)THRThe current reaches 1mA/cm2Corresponding to the applied electric field) were 0.38 and 2.21V/μm, respectively. The opening electric field is far lower than the opening electric field (2-17V/mum) of the common diamond nanowire structure reported at present and other non-metal semiconductors such as ZnO nanowire (2.4-4.6V/mum), AlN nanorod (3.8V/mum) and CdS nanowire (12.2V/mum).
2) The structure of the high-density hollow hydrogen terminal diamond nanowire with the high length-diameter ratio can be realized in one step by precisely controlling the roughness of the initial diamond film, the boron doping concentration, the etching time, the etching atmosphere and other parameters and the use of the Si substrate without adopting a multi-step method or a micro-nano mask technology and the like, so that the preparation difficulty and the complexity are greatly reduced.
Drawings
FIG. 1 is a photograph (top view) of a high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with an ultra-low field emission starting voltage threshold value prepared by the invention,
FIG. 2 is a photograph (cross-sectional view) of a high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with an ultra-low field emission starting voltage threshold value prepared by the invention,
fig. 3 shows the field emission performance of the high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with the ultra-low field emission starting voltage threshold value prepared by the invention.
Detailed Description
Detailed description of the invention
Depositing boron-doped diamond film by adopting an MPCVD system, setting the deposition temperature range to be 780 ℃, and taking CH4、 H2As the reaction gas, trimethyl borate (B (OCH)3)3) As a boron source, H2The flow rate is 300sccm, CH4The flow rate is 15sccm, H introduced into boron source2The flow rate was 20sccm, and a boron-doped diamond film was prepared. Subsequently, the diamond film was ground using diamond powders of different particle sizes of 120 μm, 60 μm, 40 μm, 30 μm, 15 μm and 5 μm in this order with a grinding disc rotating speed of 50rpm and an applied load of 100g, to a surface roughness of less than 200 nm. After precision polishing with 5 μm, 3.5 μm and 1 μm in this order, the surface roughness was about 120 nm. And (3) ultrasonically cleaning the surface of the grinded boron-doped diamond film, putting the film into a solution with the concentration of sulfuric acid to nitric acid being 5:1, and boiling for 60 min. And then, sequentially using acetone, alcohol and deionized water to ultrasonically clean the diamond film. And placing the boron-doped diamond film subjected to acid cleaning treatment in an inductively coupled plasma reaction ion device, and carrying out maskless etching together with the Si wafer under the condition of mixed gas of oxygen and chlorine. Wherein O is2And Cl2The flow rates of the two nano-wire arrays are respectively 60sccm and 30sccm, the pressure of the chamber is 1Pa, the ICP power is 200W, and the etching time is 30, so that the diamond nano-wire array group is prepared. And then, carrying out hydrogen plasma treatment on the boron-doped diamond nanowire by using an MPCVD device, and etching for 30min under the conditions that the pressure is kept at 5 kPa and the temperature is 650 ℃. And cooling to room temperature in a hydrogen atmosphere after etching. Thereby obtaining the hollow hydrogen terminal diamond nanowire array group with high density and high length-diameter ratio and ultra-low field emission starting voltage threshold.
Detailed description of the invention
Depositing boron-doped diamond film by an MPCVD system, setting the deposition temperature range to 970 ℃ and taking CH as raw material4、 H2As the reaction gas, trimethyl borate (B (OCH)3)3) As a boron source, H2The flow rate is 300sccm, CH4H with boron source introduced at a flow rate of 20sccm2The flow rate was 20sccm, and a boron-doped diamond film was prepared. Subsequently, the diamond film was ground using diamond powders of different particle sizes of 120 μm, 60 μm, 40 μm, 30 μm, 15 μm and 5 μm in this order with a grinding disc rotating speed of 100rpm and an applied load of 700g, to a surface roughness of less than 200 nm. After precision polishing with 5 μm, 3.5 μm and 1 μm in this order, the surface roughness was about 80 nm. To pairAnd (3) ultrasonically cleaning the surface of the grinded boron-doped diamond film, putting the film into a solution with the concentration of sulfuric acid to nitric acid being 5:1, and boiling for 60 min. And then, sequentially using acetone, alcohol and deionized water to ultrasonically clean the diamond film. And placing the boron-doped diamond film subjected to acid cleaning treatment in an inductively coupled plasma reaction ion device, and carrying out maskless etching together with the Si wafer under the condition of mixed gas of oxygen and chlorine. Wherein O is2And Cl2The flow rates of the two nano-wire arrays are respectively 90sccm and 10sccm, the pressure of a chamber is 4Pa, the ICP power is 200W, and the etching time is 45min, so that the diamond nano-wire array group is prepared. And then, carrying out hydrogen plasma treatment on the boron-doped diamond nanowire by using an MPCVD device, and etching for 15min under the conditions that the pressure is kept at 7kPa and the temperature is 750 ℃. And cooling to room temperature in a hydrogen atmosphere after etching. Thereby obtaining the hollow hydrogen terminal diamond nanowire array group with high density and high length-diameter ratio and ultra-low field emission starting voltage threshold.

Claims (6)

1. A method for preparing hollow diamond nano-wire array group with low field emission opening threshold is characterized in that the doping concentration is 1 multiplied by 1021cm-3To 1X 1023cm-3Controlling the surface roughness of the boron-doped diamond within the range of 80-120nm through precise grinding and polishing; then the polished boron-doped diamond film and the Si wafer are put together in O2And Cl2Performing inductively coupled plasma reactive ion etching for 20 to 90min under the condition that the gas source ratio is 2:1 to 10: 1; and then, treating the etched boron-doped diamond sheet for 5-30min by hydrogen plasma under the conditions of 5-7kPa and the temperature of 600-800 ℃, thereby obtaining the high-density high-length-diameter ratio hollow hydrogen terminal diamond nanowire array group with the ultra-low field emission starting voltage threshold value, which is used for a high-performance electron emission device.
2. The method for preparing a hollow diamond nanowire array group with a low field emission opening threshold as claimed in claim 1, characterized by comprising the following steps:
step 1: preparing a boron-doped diamond film:
depositing and preparing a boron-doped diamond film by adopting an MPCVD system;
step 2: precise grinding and polishing control of the boron-doped diamond film;
flattening the surface of the diamond film by adopting diamond grinding equipment, grinding the diamond film by using diamond powder with different particle sizes, and precisely polishing until the surface roughness is between 80 and 120 nm;
and step 3: cleaning the surface of the diamond film:
ultrasonically cleaning the surface of the grinded boron-doped diamond film to remove the residual diamond powder due to mechanical grinding; firstly, carrying out acid cleaning treatment on the cleaned boron-doped diamond film, and placing the diamond film in a sulfuric acid: heating a solution with the concentration of nitric acid of 5:1, boiling for 30-60min after the solution is boiled; then, ultrasonic cleaning is carried out on the diamond film by sequentially using acetone, alcohol and deionized water, the ultrasonic power is 50-300W, the cleaning is carried out for 25-35min each time, and the diamond film is dried; ultrasonically cleaning the diamond film for 2 times by using deionized water, wherein the ultrasonic power is 50-300W, cleaning is carried out for 25-35min each time, drying is carried out, and residual solution on the surface of the boron-doped diamond film is removed;
and 4, step 4: preparing diamond nanowires:
placing the boron-doped diamond film subjected to acid cleaning treatment and a Si wafer in an inductively coupled plasma reactive ion etching device together, and performing O-ion etching2And Cl2Carrying out maskless etching under the condition that the gas source is mixed in a ratio of 2:1 to 10:1 to prepare a diamond nanowire array group;
and 5: hydrogenation of diamond nanowires:
and (3) performing hydrogen plasma treatment on the boron-doped diamond nanowires by adopting an MPCVD device to realize surface hydrogen termination of the diamond nanowire array group.
3. The method for preparing a hollow diamond nanowire array group with a low field emission threshold as claimed in claim 2, wherein the boron-doped diamond film prepared in step 1 is prepared by setting the deposition temperature range to 740-4、H2As reaction gas, trimethyl borate(B(OCH3)3) As a boron source, H2The flow rate is 150-4Introducing H of boron source with the flow rate of 6-25sccm2The flow rate was 20 sccm.
4. The method for preparing a hollow diamond nanowire array group with a low field emission opening threshold as claimed in claim 2, wherein the precise grinding and polishing control of the boron-doped diamond film in the step 2 is as follows: in the surface flattening process, diamond powder with the grain diameters of 120 microns, 60 microns, 40 microns, 30 microns, 15 microns and 5 microns is adopted in sequence, the rotating speed of a grinding disc is 20-100rpm, the external load is 100-1000g, the diamond film is ground until the surface roughness is lower than 200nm, and then the diamond film is precisely polished by 5 microns, 3.5 microns and 1 micron until the surface roughness is 80-120 nm.
5. The method for preparing a hollow diamond nanowire array group with a low field emission threshold as claimed in claim 2, wherein the hollow diamond nanowires in step 4 are prepared by adopting an inductively coupled plasma etching method and introducing a reaction gas O2And Cl2The flow rates of the silicon nitride and the silicon nitride are respectively 30-80sccm and 3-40sccm (the mixing ratio of 2:1 to 10: 1), the pressure of the chamber is 1-9Pa, the ICP power is 200-700W, and the etching time is 30-180 min.
6. The method for preparing a hollow diamond nanowire array group with a low field emission threshold as claimed in claim 2, wherein the hydrogenation of the diamond nanowires in step 5 is performed by hydrogen plasma etching and introducing H2The flow rate is 200-; and cooling to room temperature in a hydrogen atmosphere after etching.
CN202110432576.5A 2021-02-18 2021-04-21 Preparation method of hollow diamond nanowire array group with low field emission opening threshold Pending CN113241294A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2021101877222 2021-02-18
CN202110187722 2021-02-18

Publications (1)

Publication Number Publication Date
CN113241294A true CN113241294A (en) 2021-08-10

Family

ID=77128857

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110432576.5A Pending CN113241294A (en) 2021-02-18 2021-04-21 Preparation method of hollow diamond nanowire array group with low field emission opening threshold

Country Status (1)

Country Link
CN (1) CN113241294A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101840823A (en) * 2010-05-11 2010-09-22 西北大学 Preparation method of field emission cathode of large-area nano diamond coating
CN106048524A (en) * 2016-07-11 2016-10-26 北京大学 Diamond-like nano-structure and preparation method thereof
CN110482482A (en) * 2019-07-24 2019-11-22 北京科技大学 A kind of preparation method of insulation patterns high heat-conductive diamond radiating element
CN111232972A (en) * 2020-03-19 2020-06-05 北京科技大学 Preparation method of high-performance boron-doped diamond nanowire
CN112301423A (en) * 2020-09-23 2021-02-02 中国科学院金属研究所 Preparation method of one-dimensional diamond nanocone array material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101840823A (en) * 2010-05-11 2010-09-22 西北大学 Preparation method of field emission cathode of large-area nano diamond coating
CN106048524A (en) * 2016-07-11 2016-10-26 北京大学 Diamond-like nano-structure and preparation method thereof
CN110482482A (en) * 2019-07-24 2019-11-22 北京科技大学 A kind of preparation method of insulation patterns high heat-conductive diamond radiating element
CN111232972A (en) * 2020-03-19 2020-06-05 北京科技大学 Preparation method of high-performance boron-doped diamond nanowire
CN112301423A (en) * 2020-09-23 2021-02-02 中国科学院金属研究所 Preparation method of one-dimensional diamond nanocone array material

Similar Documents

Publication Publication Date Title
CN100593842C (en) Method for preparing nanocrystalline diamond film field-effect transistor
CN109809372B (en) Method for preparing single-layer tungsten diselenide nanobelt based on space confinement strategy
CN101266919A (en) A method for selectively etching silicon nano line
Zeng et al. Field emission of silicon nanowires
TWI406807B (en) Method for making carbon nanotube film
Chang et al. Enhanced electron field emission properties from hybrid nanostructures of graphene/Si tip array
CN104831253A (en) Single granule layer nanometer diamond film with strong Si-V luminescence, and production method thereof
CN102103953A (en) Cold cathode field emission material epitaxially growing on silicon carbide substrate and method
CN102709399A (en) Manufacturing method of high-efficiency nano antenna solar battery
CN111232972B (en) Preparation method of high-performance boron-doped diamond nanowire
JP2008290888A (en) Surface treating method of silicon carbide
CN113241294A (en) Preparation method of hollow diamond nanowire array group with low field emission opening threshold
CN102502605A (en) Electrically-induced reduction method for degraded graphene oxide
Lee et al. Electrical characterizations of a controllable field emission triode based on low temperature synthesized ZnO nanowires
Li et al. Aligned rutile TiO2 nanorods: facile synthesis and field emission
Chen et al. Field emission from carbon nanosheets on pyramidal Si (100)
Baik et al. Diamond tip fabrication by air-plasma etching of diamond with an oxide mask
Kang et al. Recent development of diamond microtip field emitter cathodes and devices
US11658232B2 (en) Field effect transistor based on graphene nanoribbon and method for making the same
CN111681934B (en) Si-LaB6Composite nano field emission array cathode and preparation method thereof
US20220177313A1 (en) Graphene nanoribbon composite structure and method for making the same
CN104103470A (en) Polycrystal hexaboride annular field emission cathode and preparation method thereof
KR20170056390A (en) Method for manufacturing thin film of graphene having bandgap and thin film transistor having the thin film of graphene manufactured by the method
CN100367467C (en) Method for constructing even distributed Nano points of siliocn, Nano lines of siliocn under normal temperature
CN113604792B (en) Preparation method of diamond nano burr structure

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20210825

Address after: 100083 No. 30, Haidian District, Beijing, Xueyuan Road

Applicant after: University OF SCIENCE AND TECHNOLOGY BEIJING

Applicant after: Shunde Graduate School of Beijing University of science and technology

Address before: 100083 No. 30, Haidian District, Beijing, Xueyuan Road

Applicant before: University OF SCIENCE AND TECHNOLOGY BEIJING

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210810