CN107190246A - A kind of graphene/diamond compound film with excellent field emission performance and preparation method thereof - Google Patents
A kind of graphene/diamond compound film with excellent field emission performance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphene/diamond compound film with excellent field emission performance and preparation method thereof, belong to photoelectron material technical field.It mainly comprises the following steps 1）In the diamond thin of Grown undoped；2）In the Ni films that diamond thin Grown a layer thickness is 100 600 nm；3）Then film is made in Ar+H2Annealed in mixed atmosphere, carbon atom dissolves in Ni layers in diamond film；4）Room temperature is down to 0.5 ~ 1 DEG C/s speed, carbon atom precipitate into surface recrystallization and forms graphene, produces the graphene/diamond compound film.The present invention is directly by the use of diamond film as the presoma of graphene growth, and method is simple, it is easy to operate；Graphene can realize atomistic binding with diamond film surface in gained composite membrane, and its associativity is stronger, and stability is good.
Description
Technical field
The present invention relates to a kind of graphene/diamond compound film with excellent field emission performance and preparation method thereof, category
In technical field of semiconductors.
Background technology
Diamond is typical covalent bond structure, with hardness is high, chemical stability is good, forbidden band is wide, electronics and hole are moved
Shifting rate is high, disruptive field intensity is high, the low excellent physical and chemical performance of dielectric constant, is to prepare high reliability, long-life Flied emission
The ideal cathode material of device.However, diamond is semiconductor material with wide forbidden band, thin diamond film resistivity is very high, electronics
Difficulty is transmitted in material internal, so that the supply of electronics is difficult in conduction band so that the field emission performance of diamond is limited
System.In recent years, domestic and international researcher is attempted by growth course or using the method for ion implanting, by P, N, O, Ag, Au
It is incorporated into diamond thin to improve its electric conductivity Deng impurity.However, the thin diamond membrane conductivity after doping is low, electricity
Transport factor is low, it is difficult to as electronic device.
Graphene is by the tightly packed bi-dimensional cellular shape crystal structure constituted of flat monolayer carbon atom.In graphene planes
Interior, carbon atom is connected with hexa-atomic loop type periodic arrangement, each carbon atom by σ keys with three carbon atoms closed on, forms sp2
Hybrid structure.Carbon atom has 4 valence electrons, wherein 3 are electronically generated sp2 keys, i.e., each carbon atom contributes a non-bonding
Electronics be located at pz tracks, the pz tracks of neighbour's atom form π tracks in the direction vertical with plane, and now pi bond is partly fills up
State, pi-electron can be moved freely in graphene crystrallographic plane.This electronic structure makes graphene have excellent electrical property
Energy.Therefore prepare graphene on the diamond, to develop high field emission performance graphene/diamond compound film, realize its
Semiconductor devices, the application in the field such as field-emitter display has important scientific meaning and construction value.
In recent years, researcher have developed a variety of methods for preparing graphene, mainly including micromechanics stripping method, oxidation
Graphite reduction method, chemical vapour deposition technique etc..Wherein, the graphene function admirable that mechanical stripping method is obtained, but efficiency is very low,
Process is uncontrollable, and poor repeatability；It is due to the introducing of reducing agent although graphite oxide reducing process preparation efficiency is very high, breaks
The conjugated structure of graphene is broken, the intrinsic electric property of graphene is reduced；Chemical vapour deposition technique can prepare large area
Graphene film, but the method operating procedure is complicated, the controllability of the graphene film thickness of acquisition is poor.
The content of the invention
The present invention is intended to provide a kind of graphene/diamond compound film with excellent field emission performance, is noted by ion
Enter with the method for thermal anneal process the deposited graphite alkene film on diamond thin, simple controllable metaplasia produce high-quality graphene/
Diamond compound film；Product combines the excellent combination property of both graphene and diamond, meets filed emission cathode material
Harsh performance requirement.Another object of the present invention is to provide the preparation method of above-mentioned graphene/diamond compound film, the party
Method is simple to operation, and the excellent combination property of graphene/diamond compound film is emerged from.
The invention provides a kind of preparation method of graphene/diamond compound film with excellent field emission performance, bag
Include following steps：
（1）Diamond thin is prepared on substrate；
（2）In step（1）One layer of 100-600nm of superficial growth Ni films in obtained diamond thin；
（3）By step（2）Obtained superficial growth has the diamond film of Ni films in Ar and H2It is warming up to 800 in mixed atmosphere ~
1000 DEG C, and the carbon atom being incubated in 20-80 min, diamond film dissolves in Ni layers；
（4）Will be through step（3）The diamond film of processing is down to room temperature with 0.5 ~ 1 DEG C/s speed, and carbon atom precipitate into surface weight
Crystallize and form graphene, obtain graphene/diamond compound film.
In the above method, the step（1）Middle diamond thin can be prepared according to this area conventional method, can use microwave
Plasma activated chemical vapour deposition method, hot-wire chemical gas-phase deposition method, Dc arc plasma jet CVD chemical vapor deposition
Product method.
In the above method, the substrate is one kind in monocrystalline silicon, carborundum, molybdenum, carborundum.
In the above method, the diamond thin is micron diamond film or super nano-diamond film；
In the above method, the preparation method of micron diamond film is as follows：Using chemical vapor depsotition equipment, using purity as
99.999% H2With the CH that purity is 99.9%4For reacting gas, depositing temperature is 750 ~ 950 DEG C, and sedimentation time is 10 ~ 100h,
Prepare the micron diamond film that thickness is 5 ~ 100 μm.
In the above method, the preparation method of super nano-diamond film is as follows：Using chemical deposition equipment, using purity as
99.999% Ar and H2And the CH that purity is 99.9%4For reacting gas, depositing temperature is 750 ~ 950 DEG C, and sedimentation time is 2 ~ 10
H, prepares the super nano-diamond film that thickness is 200 nm ~ 5000nm.
In the above method, the step（2）In, the growing methods of the Ni films is magnetron sputtering, Assisted by Ion Beam is sunk
One kind in product or electron evaporation.
In the above method, the step（3）In, the diamond film that superficial growth there are Ni films is warming up to 800 ~ 1000 DEG C
Time be 25-50 min.
In the above method, the Ar and H2The volume ratio of the two in mixed atmosphere is H2：Ar =5%：95%.
In the above method, the step（4）The graphene of middle formation is individual layer, double-deck or multilayer.
The invention provides a kind of graphene/diamond compound film obtained using above-mentioned preparation method.
The present invention principle be：One layer of 100-600nm Ni films are prepared on the surface of diamond thin, and are used as growth
The presoma of graphene, diamond thin provides carbon atom；In subsequent annealing process, carbon atom dissolves in Ni substrates,
When carbon atom saturation in Ni films, the solubility for reducing carbon with temperature declines, and surface recrystallization is precipitate into from Ni films,
Form graphene.Graphene can realize atomistic binding with diamond film surface in gained composite membrane.
Beneficial effects of the present invention：
（1）The present invention only needs two processes of growth and annealing of Ni films it is achieved that method is simple, it is easy to operate；
（2）The growth course of graphene is a kind of differentiation, controllable growth in situ process certainly in the present invention, can be by controlling at heat
Manage bar part regulates and controls the number of plies of graphene；
（3）Graphene realizes atomistic binding with diamond, and stability is good；
（4）The composite membrane field emission performance prepared is good, to realizing that it leads in semiconductor devices, field-emitter display etc.
The application in domain has important scientific meaning and construction value.
Brief description of the drawings
Fig. 1 is the Raman pictures of graphene/micron diamond composite membrane prepared by embodiment 1；
Fig. 2 is the Flied emission test result figure of graphene/micron diamond composite membrane prepared by embodiment 1；
Fig. 3 is the Raman pictures of graphene/super Nano diamond composite membrane prepared by embodiment 2；
Fig. 4 is the Flied emission test result figure of graphene/super Nano diamond composite membrane prepared by embodiment 2.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1：
1）The preparation of micron diamond film：The grease of Si substrate surfaces is cleaned up successively with acetone and methanol solution first,
Then monocrystalline silicon substrate surface is ground for 5nm bortz powder using granular size, and by base in methanol solution
Piece is cleaned by ultrasonic 45min, is finally used hot blast drying, the substrate grown as micron diamond film.Using voluntarily developing
Frequency be 2.45GHz microwave plasma CVD equipment, in diameter 6cm thickness 1.2cm grown above silicon
Micron diamond film.The reacting gas ratio of experiment is H2(98.6%)/CH4(1.4%), microwave power remains 7 kW,
Gas flow rate is 406sccm, and gross pressure is 10 kPa, and temperature is 850 DEG C, and growth time is 20h, prepare grain size for 10 ~
The diamond thin of 30 μm of microns.
2）Grow Ni films：One layer of 200 nm Ni films are grown in micron diamond film surface by magnetron sputtering；
3）The growth of graphene：By step 2) prepared by the diamond film for being covered with graphene be placed in tube furnace, be evacuated to
Pressure is down to below 0.1Pa in reative cell, is passed through Ar gas and H2The mixed gas of gas controls mixed gas to standard atmospheric pressure
Flow 200sccm, 25min are warming up to 900 DEG C, are incubated 30 min, carbon atom precipitate into surface from Ni films, with 30 DEG C/min
Room temperature is dropped to, the solid solubility of carbon declines with the reduction of temperature, and enough carbon is separated out in temperature-fall period and recrystallizes to form graphite
Alkene.
4）Sample prepared by the present embodiment is analyzed：Gained graphene/micron diamond composite membrane Raman spectrums are such as
Shown in Fig. 1, the Flied emission curve of gained graphene/micron diamond composite membrane is as shown in Figure 2.
From Raman spectrums, the cm of D peak positions 1345-1, the cm of G peak positions 1584-1, the position 2701cm at 2D peaks-1, IG/ID
≈ 4 illustrates that the graphene defect that the present invention is obtained is few, and quality is high.I2D/IG≈ 1.1, and 2D peaks for it is unimodal have well it is right
Title property, it is individual layer or bilayer to illustrate graphene manufactured in the present embodiment.
Flied emission is tested in high vacuum（10-5Pa）Flied emission test system in carry out, using ito glass as anode,
Diamond film is as negative electrode, and distance is 150 μm between anode and cathode, and I-V characteristic curve is measured by Keithley 237.From
It can see in Fig. 2, the micron diamond film prepared in the present embodiment basic non-emissive electric current in test scope occurs.And this
Relatively low graphene/micron diamond composite membrane threshold electric field prepared by embodiment is 6.25V/ μm（Define at F-N flex points as unlatching
Electric field）, and obtain 0.65 mA/cm under 11.35 V/ μm of electric fields2Current density.It thus is seen that micron diamond table
The preparation of face graphene layer is remarkably improved the field emission performance of micron diamond film.
Embodiment 2
1）The preparation of super nano-diamond membrane：Using the microwave plasma chemical depositing device voluntarily developed in silicon nitrate substrate
It is upper to prepare super nano-diamond membrane.The alcohol suspending liquid of diadust (particle diameter is 0.5 μm) is used first, and nitridation silicon chip is surpassed
Acoustic shock is swung 30 minutes, is cleaned up after ultrasound with ethanol.Then silicon chip hot blast drying will be nitrogenized, it is thin as super Nano diamond
The substrate of film growth.The frequency voluntarily developed is used for 2.45 GHz microwave plasma CVD equipment, 1 ×
The 1cm super nano-diamond film of nitridation grown above silicon, experiment uses Ar, H2、CH4Mixed gas, total gas flow rate is
166sccm, wherein each gas flow is respectively：Ar is 122sccm-136sccm, H2For 24-38sccm, CH4For 6 sccm, sink
Product power is 1.0 kW, and pressure is 13 kPa, and depositing temperature is 830 DEG C, and sedimentation time is 6 h.Prepare super nanometer Buddha's warrior attendant
The nm of grain size 8 of stone film, 5 μm of thickness.
2）Grow Ni films：Use magnetically controlled sputter method in super Nano diamond superficial growth a layer thickness for 500 nm
Ni films.
3）The growth of graphene：By step 2) prepared by the diamond film for being covered with graphene be placed in tube furnace, take out true
Sky near below 0.1Pa of pressure into reative cell, is passed through Ar gas and H2The mixed gas of gas（H2(5%)：Ar(95%)）It is big to standard
Air pressure, controls the flow 200sccm, 40 min of mixed gas to be warming up to 1000 DEG C, is incubated 80 min, carbon atom is from Ni films
Surface is precipitate into, room temperature is dropped to 30 DEG C/min, the solid solubility of carbon declines with the reduction of temperature, is separated out in temperature-fall period enough
Carbon and recrystallize to form graphene.
4）Sample prepared by the present embodiment is analyzed：Gained graphene/super Nano diamond composite membrane Raman spectrums
As shown in figure 3, the Flied emission curve of gained graphene/super Nano diamond composite membrane is as shown in Figure 4.
From Raman spectrums, the cm of D peak positions 1356-1, the cm of G peak positions 1554-1, the cm of position 2660 at 2D peaks-1。I2D/
IG ≈ 0.16, it is multilayer to illustrate graphene manufactured in the present embodiment.
Flied emission is tested in high vacuum（10-5Pa）Flied emission test system in carry out, using ito glass as anode,
Diamond film is as negative electrode, and distance is 150 μm between anode and cathode, and I-V characteristic curve is measured by Keithley 237.From
It can see in Fig. 4, super nano-diamond membrane manufactured in the present embodiment basic non-emissive electric current in test scope occurs.And this
The threshold electric field of graphene/super Nano diamond composite membrane prepared by embodiment is 3.7 V/ μm than relatively low（Define F-N flex points
Locate as threshold electric field）, and obtain 71 μ A/cm under 7.3 V/ μm of electric fields2Current density.It thus is seen that super nanometer Buddha's warrior attendant
The preparation of stone surface graphene layer is remarkably improved the field emission performance of super nano-diamond membrane.
By above-described embodiment, Raman results prove to have formd graphene, and Flied emission result proves composite membrane
Emitting performance is good.
Claims (10)
1. a kind of preparation method of graphene/diamond compound film with excellent field emission performance, it is characterised in that including with
Lower step：
（1）Diamond thin is prepared on substrate；
（2）In step（1）One layer of 100-600nm of superficial growth Ni films in obtained diamond thin；
（3）By step（2）Obtained superficial growth has the diamond film of Ni films in Ar and H2It is warming up to 800 in mixed atmosphere ~
1000 DEG C, and the carbon atom being incubated in 20-80 min, diamond film dissolves in Ni layers；
（4）Will be through step（3）The diamond film of processing is down to room temperature with 0.5 ~ 1 DEG C/s speed, and carbon atom precipitate into surface weight
Crystallize and form graphene, obtain graphene/diamond compound film.
2. the preparation method of graphene/diamond compound film according to claim 1 with excellent field emission performance, its
It is characterised by：The step（1）Middle diamond thin uses microwave plasma CVD method, Hot Filament Chemical Vapor
Any of deposition process, Dc arc plasma jet CVD chemical gaseous phase depositing process are prepared from.
3. the preparation method of graphene/diamond compound film according to claim 1 with excellent field emission performance, its
It is characterised by：The substrate is one kind in monocrystalline silicon, carborundum, molybdenum, carborundum.
4. the preparation method of graphene/diamond compound film according to claim 1 with excellent field emission performance, its
It is characterised by：The diamond thin is micron diamond film or super nano-diamond film.
5. the preparation method of graphene/diamond compound film according to claim 4 with excellent field emission performance, its
It is characterised by：The preparation method of micron diamond film is as follows：Using chemical vapor depsotition equipment, using purity as 99.999%
H2With the CH that purity is 99.9%4For reacting gas, depositing temperature is 750 ~ 950 DEG C, and sedimentation time is 10 ~ 100h, is prepared
Thickness is 5 ~ 100 μm of micron diamond film.
6. the preparation method of graphene/diamond compound film according to claim 4 with excellent field emission performance, its
It is characterised by：The preparation method of super nano-diamond film is as follows：Using chemical deposition equipment, the Ar using purity as 99.999%
And H2And the CH that purity is 99.9%4For reacting gas, depositing temperature is 750 ~ 950 DEG C, and sedimentation time is 2 ~ 10 h, is prepared
Thickness is 200 nm ~ 5000nm super nano-diamond film.
7. the preparation method of graphene/diamond compound film according to claim 1 with excellent field emission performance, its
It is characterised by：The step（2）In, the growing method of the Ni films is that magnetron sputtering, ion beam assisted depositing or electronics steam
One kind in hair.
8. the preparation method of graphene/diamond compound film according to claim 1 with excellent field emission performance, its
It is characterised by：The step（3）In, the time that the diamond film that superficial growth has Ni films is warming up into 800 ~ 1000 DEG C is
25-50 min；The Ar and H2The volume ratio of the two in mixed atmosphere is 95:5.
9. the preparation method of graphene/diamond compound film according to claim 1 with excellent field emission performance, its
It is characterised by：The step（4）The graphene of middle formation is individual layer, double-deck or multilayer.
10. graphene/diamond compound film that one kind is obtained using the preparation method described in any one of claim 1 ~ 9.
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Cited By (11)
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| CN109273354A (en) * | 2018-09-07 | 2019-01-25 | 中国电子科技集团公司第十三研究所 | Diamond device and preparation method thereof |
| CN109722642A (en) * | 2017-10-30 | 2019-05-07 | 深圳先进技术研究院 | Equipped with diamond/graphene the compound lubricating film workpiece and preparation method thereof |
| CN109722641A (en) * | 2017-10-30 | 2019-05-07 | 深圳先进技术研究院 | Diamond/graphene composite heat conduction film and preparation method thereof and cooling system |
| CN110550869A (en) * | 2019-10-12 | 2019-12-10 | 北京大学 | Method for preparing graphene glass with assistance of ion implantation and graphene glass |
| CN111058011A (en) * | 2019-12-25 | 2020-04-24 | 浙江工业大学 | Nano-diamond-graphene composite film electrode and preparation method thereof |
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| CN111517305A (en) * | 2020-04-08 | 2020-08-11 | 北京科技大学 | Preparation method of graphene/diamond composite structure with high carrier concentration |
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| CN113881929A (en) * | 2021-09-15 | 2022-01-04 | 湖南新锋先进材料科技有限公司 | Diamond-graphene film with double-sided structure and preparation method and application thereof |
| CN113881929B (en) * | 2021-09-15 | 2024-04-02 | 湖南新锋先进材料科技有限公司 | Diamond-graphene film with double-sided structure, and preparation method and application thereof |
| CN114959699A (en) * | 2022-08-02 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | Low-friction metal/ultra-nano diamond composite coating and preparation method thereof |
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