CN105967174A - Method for growing graphene on sapphire substrate - Google Patents
Method for growing graphene on sapphire substrate Download PDFInfo
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- CN105967174A CN105967174A CN201610310853.4A CN201610310853A CN105967174A CN 105967174 A CN105967174 A CN 105967174A CN 201610310853 A CN201610310853 A CN 201610310853A CN 105967174 A CN105967174 A CN 105967174A
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- Prior art keywords
- sapphire substrate
- growing graphene
- hydrocarbon
- method growing
- hydrogen
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Abstract
The invention discloses a method for growing graphene on a sapphire substrate. The method comprises the following steps: putting the sapphire substrate in a chemical vapor deposition reaction furnace; pumping hydrogen in the reaction furnace, and carrying out annealing and cleaning treatment on the sapphire substrate; pumping a mixed gas of hydrocarbon and an inert gas; pumping hydrogen in the reaction furnace, and carrying out annealing treatment on the sapphire substrate, thus obtaining a graphene film layer. According to the method disclosed by the invention, a graphene layer grows on the sapphire substrate, a molecular bond with weaker bond energy is formed at an interface connecting position of the sapphire substrate and nitride, no-damage peeling of epitaxial layer of the nitrate and the sapphire substrate is facilitated, the sapphire substrate is enabled to be repeatedly used, and the using cost of the sapphire substrate is reduced.
Description
Technical field
The invention belongs to Light-Emitting Diode technical field, particularly relate to one and grow graphite on a sapphire substrate
The method of alkene.
Background technology
Visible light emitting diode (LED) based on III nitride semiconductor have length in service life,
Energy-saving and environmental protection, high reliability, the field such as the most colored display, backlight and illumination
On application more and more universal.Owing to lacking the homogeneity substrate being applicable to large-scale production, nitride is partly led
Body light emitting epitaxial layer commonly uses heterogeneousization substrate, such as sapphire (Al2O3), SiC or Si etc., due to
Epitaxial growth technology maturation in Sapphire Substrate, properties of product are preferable, and price has the most excellent compared with SiC
Gesture, major part LED extension manufacturer all uses it as epitaxial wafer growth substrates.
Along with developing rapidly of market in recent years, the production cost reducing LED becomes epitaxial growth skill
One of important directions of art development, using large scale (more than 4 inches) Sapphire Substrate is a kind of effectively fall
The approach of low extension cost.Along with the increase of substrate dimension, substrate is as realized reusing, by permissible
Reduce further extension cost, and reduce and manufacture the consumption of energy consumption needed for sapphire, reach environmental protection
Purpose.But owing to GaN and Sapphire Substrate have the strongest bonding force, it is difficult to realize nitride epitaxial layer with
The separation of initial substrate.Sapphire and epitaxial layer are separated by the most general employing laser lift-off technique, but
Certain damage costly, and is caused after peeling off in interface by laser lift-off equipment, needs to carry out substrate
Subsequent treatment, adds the substrate yield after the complexity of technique, and stripping low, is unfavorable for repeating to make
With.
In order to solve problem above, it is thin that industry puts forward to shift Graphene between Sapphire Substrate and epitaxial layer
The technology of film.Graphene is a kind of two dimension conductive material, is connected to by sp2 electron orbit between carbon atom
Together.Generally, grapheme material is made up of one or more layers, has electricity, calorifics and the mechanics machine of excellence
Tool performance.Graphene layer is increased so that graphene layer and nitride are at interface even between epitaxial layer and substrate
Meeting place and form the molecular link that bond energy is more weak, the not damaged for nitride epitaxial layer and Sapphire Substrate peels off offer
Condition.
Prior art utilizes chemical vapour deposition technique by graphene growth on foil, then use
Polymer is covered on graphene layer as supporting layer, re-uses chemical solution and dissolves or erode metal foil
Sheet, then will be attached to the graphene layer on polymer and transfer in Sapphire Substrate, finally use chemical solution
Polymeric support layer is removed in agent, so that having graphene layer on substrate.Although this technology can be on substrate
Form Graphene, make between nitride epitaxial layer with Graphene, to there is more weak molecular link and be connected, in order to
Separate with Sapphire Substrate in nitride epitaxial layer, but this technique needs to grow on present foil stone
Ink alkene, then Graphene is shifted, processing step is complicated, and cost is high.
Summary of the invention
It is an object of the invention to provide a kind of method growing Graphene on a sapphire substrate, make nitride
Epitaxial layer can separate with the not damaged of Sapphire Substrate, to improve the reusing of substrate.
To achieve these goals, the present invention takes following technical solution:
A kind of method growing Graphene on a sapphire substrate, comprises the following steps:
Step 1, Sapphire Substrate is inserted in chemical vapour deposition reactor furnace；
Step 2, in reacting furnace, it is passed through hydrogen, Sapphire Substrate is cleaned, makes annealing treatment；
Step 3, it is passed through the mixed gas of Hydrocarbon and noble gas to reacting furnace；
Step 4, in reacting furnace, it is passed through hydrogen, makes annealing treatment under Sapphire Substrate, obtain graphite
Alkene film layer.
More specifically, in described step 1, the temperature in reacting furnace is 1300～1600 DEG C, and pressure is
≥1mTorr。
More specifically, described Hydrocarbon is methane, ethane, acetylene, ethylene, the one of ethanol or
More than Zhong.
More specifically, the bulk purity of described noble gas and hydrocarbon gas is more than 99%.
More specifically, in the mixed gas of described Hydrocarbon and noble gas, Hydrocarbon and hydrogen
Mol ratio be 0.005～1.
More specifically, described noble gas is argon.
More specifically, when in described step 2 being cleaned Sapphire Substrate, reaction in-furnace temperature is
1100～1200 DEG C, the flow velocity of hydrogen is 70～150L/min, keeps 5～20min.
More specifically, in described step 2, the cooling rate of annealing is 70～80 DEG C/min, will be cooled to
800～1000 DEG C.
More specifically, in described step 3, the flow velocity of Hydrocarbon is 10～100sccm, inert gas flow
Speed is 200～500sccm, and temperature is 800～1000 DEG C, keeps 20～40 minutes.
More specifically, described step 4 makes annealing treatment under 500～800 DEG C of temperature conditionss, hydrogen
Flow is 3～5L/min, keeps 1～3min, and cooling rate is 70～80C/min, is cooled to room temperature.
From above technical scheme, the present invention, by growing graphene layer on a sapphire substrate, utilizes stone
The feature that ink alkene layer is more weak with nitride epitaxial interlayer molecular link bond energy, beneficially substrate and the stripping of epitaxial layer
From, to reach to reuse substrate, reduce the purpose of cost, and technique is simpler.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention LED chip.
Detailed description of the invention
In order to above and other objects of the present invention, feature and advantage can be become apparent from, the present invention cited below particularly
Embodiment is described below in detail.
Graphene has the atom case of Hexagonal Close-packed, each layer atom with the element nitride crystal of wurtzite structure
Arrangement situation identical, on Graphene, therefore carry out nitride epitaxial growth can realize higher crystal matter
Amount.Meanwhile, by adding graphene layer so that it is with nitride in more weak the dividing of formation bond energy of junction, interface
The not damaged of sub-key, beneficially nitride epitaxial layer and Sapphire Substrate is peeled off, the basic think of of the inventive method
Road is direct growth graphene layer on a sapphire substrate, the most again at graphene layer growing epitaxial layers,
On the basis of Simplified flowsheet, the stripping for Sapphire Substrate with epitaxial layer provides condition, makes substrate repeatedly to make
With, reduce substrate use cost.
It is above the core concept of the application, below in conjunction with the accompanying drawing in the embodiment of the present invention, to the present invention
The technical scheme of embodiment is clearly and completely described, it is clear that described embodiment is only this
Bright a part of embodiment rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff obtains under not making creative work premise, broadly falls into the present invention
The scope of protection.
Elaborate a lot of detail in the following description so that fully understanding the present invention, but the present invention
Other can also be used to be different from alternate manner described here implement, those skilled in the art can be not
Doing similar popularization in the case of running counter to intension of the present invention, therefore the present invention is not by following public specific embodiment
Restriction.
Secondly, the present invention combines schematic diagram and is described in detail, when describing the embodiment of the present invention in detail, for ease of
Illustrate, represent that the accompanying drawing of device architecture can be disobeyed general ratio and be done partial enlargement, and described schematic diagram is simply
Example, it should not limit the scope of protection of the invention at this.It should be noted that accompanying drawing all uses the simplest
The form changed and all use non-ratio accurately, only in order to convenient, clearly aid in illustrating the embodiment of the present invention
Purpose.
The present invention uses the chemical vapour deposition technique of Hydrocarbon to grow one layer or two-layer on a sapphire substrate
Graphene, comprises the following steps:
Step 1, inserting in chemical vapour deposition reactor furnace by Sapphire Substrate, the temperature in reacting furnace is
1300～1600 DEG C, pressure is >=1mTorr；
Step 2, in reacting furnace, it is passed through hydrogen, Sapphire Substrate is cleaned, makes annealing treatment；Specifically
, during cleaning, the flow velocity of the hydrogen being passed through in reacting furnace is 70～150L/min, and reaction in-furnace temperature is
1100～1200 DEG C, keep 5～20min, after completing cleaning, 800～1000 DEG C will be cooled to, cooling speed
Degree is 70～80 DEG C/min；
Step 3, being passed through the mixed gas of Hydrocarbon and noble gas to reacting furnace, noble gas is carbon
The carrier of hydrogen compound, the noble gas of the present embodiment is argon；Concrete, the flow velocity of Hydrocarbon is
10～100sccm, noble gas flow velocity is 200～500sccm, and temperature is 800～1000 DEG C, keeps
20～40 minutes, sccm represented standard milliliters per minute；
Step 4, in reacting furnace, it is passed through hydrogen, makes annealing treatment under 500～800 DEG C of temperature conditionss,
Obtain graphene film layer；Concrete, the flow of hydrogen is 3～5L/min, keeps 1～3min, then drops
Warming to room temperature, cooling rate is 70～80C/min.
The Hydrocarbon of the present invention be the one in methane, ethane, acetylene, ethylene, ethanol or one with
On, the bulk purity of noble gas and hydrocarbon gas is more than 99%, Hydrocarbon and noble gas
Mixed gas in, the mol ratio of Hydrocarbon and hydrogen is 0.005～1.
As it is shown in figure 1, after growing graphene layer 200 in Sapphire Substrate 100, at graphene layer 200
Upper continued growth nitride epitaxial layer, nitride AlxInyGa1-x-yN(0≤x,y≤1；X+y≤1) epitaxial layer
Growth can realize nitride epitaxial layer in the middle of Metalorganic chemical vapor deposition (MOCVD) reaction chamber
Succession be: N-type buffer layer 300, N-shaped electron injecting layer 400, active layer 500 and p-type are empty
Cave implanted layer 600；Make the metal thick film of more than two-layer in p-type hole injection layer 600 side, form p
Type electrode 700.
Make nitride epitaxial layer time, by control organic metal source of the gas, as trimethyl gallium (TMGa),
Trimethyl aluminium (TMAl), trimethyl indium (TMIn) etc., and the regulation work such as heating-up temperature, chamber pressure
Skill parameter controls the materials such as the chemical constituent of nitride, thickness, crystal mass, doping content, surface topography
Material characterisitic parameter, if heating temperature range is 450～1300 DEG C, chamber pressure scope be 0.01～
750Torr。
Further, the making step of p-type electrode 700 is as follows: use physical vapour deposition (PVD) (PVD) side
Method, is deposited with Ni/Au, forms ohmic contact layer on p-type hole injection layer 600 surface；PVD is used to set
The standby reflecting layer making the metallic films such as Ag, Al on ohmic contact layer；Then Ni or Ti/W etc. is made
The barrier layer of metallic film；Finally make the supporting layer of the metal thick film such as Cu, Al.PVD equipment is electron beam
Evaporation (EBV) or magnetron sputtering (MS) equipment.
The present invention, by direct growth graphene layer on a sapphire substrate, grows on graphene layer the most again
Epitaxial layer, owing to graphene layer and nitride are more weak at the bond energy of junction, interface molecular link, can use machinery
Sapphire Substrate and nitride epitaxial layer are separated by the mode peeled off:
Wafer device is placed on bonding apparatus, uses vacuum chuck device to adsorb respectively in Sapphire Substrate
Bottom and p-type top of electrodes, when two vacuum chuck device occurred levels or the relative displacement of vertical direction
Time, wafer device can separate at graphene layer, and the Sapphire Substrate after separation can be conventional by industry
Finishing method is by after surface finish, so that it may reach the reusable purpose of substrate.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses this
Invention.Multiple amendment to these embodiments will be apparent for those skilled in the art
, generic principles defined herein can without departing from the spirit or scope of the present invention,
Other embodiments realizes.Therefore, the present invention is not intended to be limited to embodiment illustrated herein, and is intended to
Meet the widest range consistent with principles disclosed herein and features of novelty.
Claims (10)
1. the method growing Graphene on a sapphire substrate, it is characterised in that include following step
Rapid:
Step 1, Sapphire Substrate is inserted in chemical vapour deposition reactor furnace；
Step 2, in reacting furnace, it is passed through hydrogen, Sapphire Substrate is cleaned, makes annealing treatment；
Step 3, it is passed through the mixed gas of Hydrocarbon and noble gas to reacting furnace；
Step 4, in reacting furnace, it is passed through hydrogen, makes annealing treatment under Sapphire Substrate, obtain graphite
Alkene film layer.
2. the method growing Graphene as claimed in claim 1 on a sapphire substrate is characterized in that:
In described step 1, the temperature in reacting furnace is 1300～1600 DEG C, and pressure is >=1mTorr.
3. the method growing Graphene on a sapphire substrate as claimed in claim 1, its feature exists
In: described Hydrocarbon be methane, ethane, acetylene, ethylene, ethanol one or more.
4. the method growing Graphene on a sapphire substrate as claimed in claim 1, its feature exists
In: the bulk purity of described noble gas and hydrocarbon gas is more than 99%.
5. the method growing Graphene on a sapphire substrate as claimed in claim 1, its feature exists
In: in the described Hydrocarbon mixed gas with noble gas, Hydrocarbon with the mol ratio of hydrogen is
0.005～1.
6. the method growing Graphene on a sapphire substrate as claimed in claim 1, its feature exists
In: described noble gas is argon.
7. the method growing Graphene on a sapphire substrate as claimed in claim 1, its feature exists
In: when in described step 2 being cleaned Sapphire Substrate, reaction in-furnace temperature is 1100～1200 DEG C,
The flow velocity of hydrogen is 70～150L/min, keeps 5～20min.
8. the method growing Graphene on a sapphire substrate as described in claim 1 or 7, its feature
Be: in described step 2 annealing cooling rate be 70～80 DEG C/min, will be cooled to 800～
1000℃。
9. the method growing Graphene on a sapphire substrate as claimed in claim 1, its feature exists
In: in described step 3, the flow velocity of Hydrocarbon is 10～100sccm, noble gas flow velocity be 200～
500sccm, temperature is 800～1000 DEG C, keeps 20～40 minutes.
10. the method growing Graphene on a sapphire substrate as described in claim 1 or 7, its feature
Being: make annealing treatment under 500～800 DEG C of temperature conditionss in described step 4, the flow of hydrogen is
3～5L/min, keep 1～3min, cooling rate is 70～80C/min, is cooled to room temperature.
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| CN201610310853.4A CN105967174A (en) | 2016-05-11 | 2016-05-11 | Method for growing graphene on sapphire substrate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107689323A (en) * | 2017-08-11 | 2018-02-13 | 北京大学 | A kind of graphene Sapphire Substrate for being applied to III group-III nitride epitaxial growth |
| CN107804842A (en) * | 2017-10-24 | 2018-03-16 | 南昌航空大学 | Surface treatment method based on sapphire substrates growth graphene |
| CN107872550A (en) * | 2017-11-03 | 2018-04-03 | 广东美晨通讯有限公司 | Display panel and its substrate manufacture |
| CN109081332A (en) * | 2018-08-24 | 2018-12-25 | 北京石墨烯研究院 | Graphene nano graphical sapphire substrate and preparation method thereof |
| CN109502575A (en) * | 2018-12-25 | 2019-03-22 | 江苏鲁汶仪器有限公司 | A kind of method of chemical vapor deposition preparation large-area graphene |
| CN112086343A (en) * | 2020-08-24 | 2020-12-15 | 中国科学院长春光学精密机械与物理研究所 | Hexagonal boron nitride film growth method and hexagonal boron nitride film |
| CN113394306A (en) * | 2021-05-18 | 2021-09-14 | 浙江大学 | Reusable ZnO single crystal substrate based on graphene and method for preparing ZnO film |
| CN113981542A (en) * | 2021-11-02 | 2022-01-28 | 山东大学 | Method for preparing high-quality single-crystal-domain two-dimensional material by regulating and controlling cavity pressure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102915913A (en) * | 2012-10-22 | 2013-02-06 | 西安电子科技大学 | Graphene CVD (chemical vapor deposition) direct epitaxial growth method based on sapphire substrate and device fabricated with method |
| CN104045079A (en) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | Method for epitaxially growing graphene on sapphire/epitaxial metal interface |
-
2016
- 2016-05-11 CN CN201610310853.4A patent/CN105967174A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102915913A (en) * | 2012-10-22 | 2013-02-06 | 西安电子科技大学 | Graphene CVD (chemical vapor deposition) direct epitaxial growth method based on sapphire substrate and device fabricated with method |
| CN104045079A (en) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | Method for epitaxially growing graphene on sapphire/epitaxial metal interface |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107689323A (en) * | 2017-08-11 | 2018-02-13 | 北京大学 | A kind of graphene Sapphire Substrate for being applied to III group-III nitride epitaxial growth |
| CN107804842A (en) * | 2017-10-24 | 2018-03-16 | 南昌航空大学 | Surface treatment method based on sapphire substrates growth graphene |
| CN107872550A (en) * | 2017-11-03 | 2018-04-03 | 广东美晨通讯有限公司 | Display panel and its substrate manufacture |
| CN109081332A (en) * | 2018-08-24 | 2018-12-25 | 北京石墨烯研究院 | Graphene nano graphical sapphire substrate and preparation method thereof |
| CN109081332B (en) * | 2018-08-24 | 2020-12-08 | 北京石墨烯研究院 | Graphene nano-patterned sapphire substrate and preparation method thereof |
| CN109502575A (en) * | 2018-12-25 | 2019-03-22 | 江苏鲁汶仪器有限公司 | A kind of method of chemical vapor deposition preparation large-area graphene |
| CN109502575B (en) * | 2018-12-25 | 2021-09-21 | 江苏鲁汶仪器有限公司 | Method for preparing large-area graphene through chemical vapor deposition |
| CN112086343A (en) * | 2020-08-24 | 2020-12-15 | 中国科学院长春光学精密机械与物理研究所 | Hexagonal boron nitride film growth method and hexagonal boron nitride film |
| CN113394306A (en) * | 2021-05-18 | 2021-09-14 | 浙江大学 | Reusable ZnO single crystal substrate based on graphene and method for preparing ZnO film |
| CN113981542A (en) * | 2021-11-02 | 2022-01-28 | 山东大学 | Method for preparing high-quality single-crystal-domain two-dimensional material by regulating and controlling cavity pressure |
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