CN102915913B - Graphene CVD (chemical vapor deposition) direct epitaxial growth method based on sapphire substrate and device fabricated with method - Google Patents
Graphene CVD (chemical vapor deposition) direct epitaxial growth method based on sapphire substrate and device fabricated with method Download PDFInfo
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- CN102915913B CN102915913B CN201210408274.5A CN201210408274A CN102915913B CN 102915913 B CN102915913 B CN 102915913B CN 201210408274 A CN201210408274 A CN 201210408274A CN 102915913 B CN102915913 B CN 102915913B
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Abstract
The invention discloses a graphene CVD (chemical vapor deposition) direct epitaxial growth method based on a sapphire substrate. Sapphire is used as the substrate, the sapphire substrate is reasonably pre-processed, and the growth pressure, the flow rate and the temperature are regulated, so that the graphene can directly grow on the sapphire without metals as the catalyst, and the grown graphene can be directly used to fabricate various devices without being transferred, so that the electrical characteristics and reliability of the device can be enhanced, and the complexity of fabrication of the device can be reduced. The large-area graphene material with semiconductor cleanliness is grown, the controllability of a single layer is more than 80%, and the area of a wafer is up to 8 inches.
Description
Technical field
The invention belongs to semi-conducting material and manufacture field, relate to key technology prepared by semi-conducting material, particularly the controlled epitaxial growth method of a kind of large-area graphene based on Sapphire Substrate, can be used for the preparation of the large area wafer level grapheme material without the need to transfer.
Background technology
Along with the development of integrated circuit, the critical size of current silicon (Si) base device has reached the theory and technology limit, and quantum effect has become main restriction scheme.Grapheme material is a kind of carbon back two dimensional crystal, and be known the thinnest the lightest material at present, individual layer only atomic thickness, it has extremely excellent physicochemical properties, and (theory is estimated to exceed 200000cm to such as high carrier mobility
2v
-1s
-1it is hundreds of times of Si), superpower mechanical performance (Young's modulus is about 1000GPa), high specific area and fabulous gas-sensitive property, the high transparency and pliability, and there is not mismatch problems in it and substrate, can be completely compatible with Si base device technique, there is outstanding industrial advantage.Therefore, Graphene appear as industrial circle and scientific and technological circle bring dawn, it is the new material that the alternative Si be expected most becomes base semiconductor material of future generation.
Although Graphene has so excellent character, in the preparation of Graphene, still there is key issue much urgently to be resolved hurrily at present.The wafer level graphene growing method of main flow is based on transition metal-catalyzed CVD in the world at present, can be used for the preparation of large-area graphene, and not by the restriction of substrate dimension, equipment is simple.A shortcoming the most significant to use metal catalytic substrate, therefore be difficult to Graphene to clean and transfer to other and be applicable in the dielectric substrate of device, and the residue remained in after transfer process on Graphene or pollutant will reduce the mobility of Graphene, thus affect the electrology characteristic of graphene device.Therefore, the restriction of prior art must be broken through, courageously break through technique, explore new substrate, realize the clean graphene growth method of large area without transfer.
Sapphire is usually used as the substrate of various Material growth, and sapphire is a kind of insulating material, has high stability in the case of a high temperature, and has hexagonal structure.Sapphire material as substrate, mainly due to its low cost, the features such as large area.In addition, there is kinds of surface in Sapphire Substrate, and as c face, a face, r face etc., therefore can grow the material of multiple different structure, can study the impact of various substrates on material behavior.In a word, sapphire has far-reaching potentiality in semi-conducting material manufacture and device manufacturing processes.
Graphene is six side's honeycombs, and lattice constant is 0.246nm, and buergerite sapphire is also hexagonal structure, and lattice constant is 0.4758nm, and the lattice mismatch of the two is comparatively large, is about 50%.The experiment of the people such as H.J.Song shows that larger lattice mismatch is conducive to the growth of Graphene, see Large scale metal-free synthesis of graphene on sapphire and transfer-free device fabrication.Nanoscale, V4, p3050 (2012).In order to be combined with Graphene by sapphire, and without Graphene transfer process, to obtain high-quality large-area graphene material, be necessary that research directly carries out Graphene CVD epitaxial growth on a sapphire substrate.
Summary of the invention
The object of the invention is to overcome the deficiency in existing large-area graphene growing technology, propose a kind of large-area high-quality graphene growth method without the need to transfer based on Sapphire Substrate, to improve the electrology characteristic of Graphene and device.
Realizing key problem in technology of the present invention is: adopt sapphire as substrate, by carrying out rational preliminary treatment to Sapphire Substrate, growth regulation pressure, flow and temperature, on sapphire face direct growth Graphene, without the need to metal as catalyst, the Graphene of growth, without the need to transfer process, just can be directly used in and manufacture various device, improve the electrology characteristic of device, reliability, reduces the complexity that device manufactures.Its growing method performing step comprises as follows:
(1) Sapphire Substrate is successively put into acetone, clean in ethanol and deionized water, each time 5 ~ 10min, takes out substrate from deionized water, dries up with high pure nitrogen (99.9999%);
(2) Sapphire Substrate is put into chemical vapor deposition CVD reative cell, extracting vacuum to 10
-5~ 10
-6torr, to remove the residual gas in reative cell;
(3) in reative cell, H is passed into
2carry out substrate surface preliminary treatment, gas flow 1 ~ 20sccm, reative cell vacuum degree 0.1 ~ 1Torr, underlayer temperature 900 ~ 1000 DEG C, processing time 5 ~ 10min;
(4) in reative cell, Ar and CH is passed into
4, keep Ar and CH
4flow-rate ratio be 10: 1 ~ 2: 1, Ar flow, 20 ~ 200sccm, CH
4flow 1 ~ 20sccm, air pressure maintains 0.1 ~ 1atm, temperature 1000 ~ 1200 DEG C, heating-up time 20 ~ 60min, retention time 30 ~ 60min;
(5) Temperature fall is to less than 100 DEG C, keeps Ar and CH in operation (5)
4flow is constant, air pressure 0.1 ~ 1atm, completes the growth of Graphene.
Through above operation, can grow the large-area graphene material with semiconductor cleanliness factor, the controllability of individual layer is more than 80%, and disk area is maximum can to 8 inches.
Tool of the present invention has the following advantages:
1., owing to adopting sapphire as substrate, the Graphene of growth just may be used for the manufacture of device without the need to transfer, improve reliability and the electrology characteristic of device.
2., owing to adopting sapphire as substrate, simplify graphene growth step and device fabrication step, reduce Graphene manufacturing cost.
Accompanying drawing explanation
Fig. 1 is the graphene growth flow chart based on Sapphire Substrate of the present invention;
Fig. 2 is the graphene growth procedure structure schematic diagram based on Sapphire Substrate of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and be not used in restriction invention.
Embodiment
With reference to Fig. 1, the present invention provides following embodiment:
Embodiment 1:
Performing step of the present invention is as follows:
Step 1, Sapphire Substrate prepares.
Sapphire Substrate is successively put into acetone, and clean in ethanol and deionized water, each time 10min, takes out substrate from deionized water, dries up with high pure nitrogen (99.9999%).
Step 2, reative cell vacuumizes.
The Sapphire Substrate of semiconductor device levels is placed in chemical vapor deposition CVD reative cell, extracting vacuum to 10
-6torr, to remove the residual gas in reative cell.
Step 3, sapphire substrate surface preliminary treatment.
H is passed in reative cell
2carry out substrate surface preliminary treatment, gas flow 2sccm, reative cell vacuum degree 0.1Torr, underlayer temperature 950 DEG C, processing time 5min.
Step 4, Graphene CVD epitaxial growth.
Ar and CH is passed in reative cell
4, keep Ar and CH
4flow-rate ratio be 10: 1, Ar flow 20sccm, CH
4flow 2sccm, air pressure maintains 0.5atm, temperature 1200 DEG C, heating-up time 20min, retention time 50min.
Step 5, cooling procedure.
Temperature fall, to less than 100 DEG C, keeps Ar and CH in operation (4)
4flow is constant, air pressure 0.5atm, completes the growth of Graphene.
Embodiment 2:
Performing step of the present invention is as follows:
Steps A, Sapphire Substrate prepares.
Sapphire Substrate is successively put into acetone, and clean in ethanol and deionized water, each time 10min, takes out substrate from deionized water, dries up with high pure nitrogen (99.9999%).
Step B, reative cell vacuumizes.
The Sapphire Substrate of semiconductor device levels is placed in chemical vapor deposition CVD reative cell, extracting vacuum to 10
-6torr, to remove the residual gas in reative cell.
Step C, sapphire substrate surface preliminary treatment.
H is passed in reative cell
2carry out substrate surface preliminary treatment, gas flow 5sccm, reative cell vacuum degree 0.2Torr, underlayer temperature 950 DEG C, processing time 10min.
Step D, Graphene CVD epitaxial growth.
Ar and CH is passed in reative cell
4, keep Ar and CH
4flow-rate ratio be 8: 1, Ar flow 40sccm, CH
4flow 5sccm, air pressure maintains 0.2atm, temperature 1100 DEG C, heating-up time 20min, retention time 30min.
Step e, cooling procedure.
Temperature fall, to less than 100 DEG C, keeps Ar and CH in operation (D)
4flow is constant, air pressure 0.2Torr, completes the growth of Graphene.
Embodiment 3:
Performing step of the present invention is as follows:
Step one, Sapphire Substrate prepares.
Sapphire Substrate is successively put into acetone, and clean in ethanol and deionized water, each time 8min, takes out substrate from deionized water, dries up with high pure nitrogen (99.9999%).
Step 2, reative cell vacuumizes.
The Sapphire Substrate of semiconductor device levels is placed in chemical vapor deposition CVD reative cell, extracting vacuum to 10
-6torr, to remove the residual gas in reative cell.
Step 3, sapphire substrate surface preliminary treatment.
H is passed in reative cell
2carry out substrate surface preliminary treatment, gas flow 5sccm, reative cell vacuum degree 0.2Torr, underlayer temperature 1000 DEG C, processing time 8min.
Step 4, Graphene CVD epitaxial growth.
Ar and CH is passed in reative cell
4, keep Ar and CH
4flow-rate ratio be 6: 1, Ar flow 60sccm, CH
4flow 10sccm, air pressure maintains 0.2atm, temperature 1000 DEG C, heating-up time 20min, retention time 40min.
Step 5, cooling procedure.
Temperature fall, to less than 100 DEG C, keeps Ar and CH in operation (three)
4flow is constant, air pressure 0.2atm, completes the growth of Graphene.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (1)
1., based on the direct epitaxial growth method of Graphene CVD of Sapphire Substrate, it is characterized in that,
Adopt sapphire as substrate, by carrying out rational preliminary treatment to Sapphire Substrate, growth regulation pressure, flow and temperature, on sapphire face direct growth Graphene, without the need to metal as catalyst, the Graphene of growth, without the need to transfer process, just can be directly used in and manufacture various device;
Its growing method performing step comprises as follows:
(1) Sapphire Substrate is successively put into acetone, clean in ethanol and deionized water, each time 5 ~ 10min, takes out substrate, dries up with high pure nitrogen from deionized water;
(2) Sapphire Substrate is put into chemical vapor deposition reaction chamber, extracting vacuum to 10
-5~ 10
-6torr, to remove the residual gas in reative cell;
(3) in reative cell, H is passed into
2carry out substrate surface preliminary treatment;
(4) in reative cell, Ar and CH is passed into
4;
(5) Temperature fall is to less than 100 DEG C, keeps Ar and the CH4 flow in operation (5) constant, completes the growth of Graphene;
In described step (3), in reative cell, pass into H
2carry out substrate surface preliminary treatment, gas flow 1 ~ 20sccm, reative cell vacuum degree 0.1 ~ 1Torr, underlayer temperature 900 ~ 1000 DEG C, processing time 5 ~ 10min;
In described step (3), in reative cell, pass into Ar and CH
4, keep Ar and CH
4flow-rate ratio be 10: 1 ~ 2: 1, Ar flow, 20 ~ 200sccm, CH
4flow 1 ~ 20sccm, air pressure maintains 0.1 ~ 1atm, temperature 1000 ~ 1200 DEG C, heating-up time 20 ~ 60min, retention time 30 ~ 60min;
In described step (5), Temperature fall, to less than 100 DEG C, keeps Ar and CH in operation (5)
4flow is constant, air pressure 0.1 ~ 1atm, completes the growth of Graphene.
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| CN107541714A (en) * | 2016-06-24 | 2018-01-05 | 北京大学 | A kind of method for fast growing of big size graphene glass |
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| 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 |
| WO2016149934A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院上海微系统与信息技术研究所 | Growing method for graphene |
| CN105576086B (en) * | 2015-12-21 | 2017-11-07 | 曹胜伟 | A kind of compound substrate of growing gallium nitride crystal and preparation method thereof |
| CN105967174A (en) * | 2016-05-11 | 2016-09-28 | 芜湖德豪润达光电科技有限公司 | Method for growing graphene on sapphire substrate |
| CN107804842A (en) * | 2017-10-24 | 2018-03-16 | 南昌航空大学 | Surface treatment method based on sapphire substrates growth graphene |
| CN107827101A (en) * | 2017-12-14 | 2018-03-23 | 天通银厦新材料有限公司 | A kind of method for growing graphene on a sapphire substrate |
| 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 |
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Non-Patent Citations (2)
| Title |
|---|
| Characterization of Graphene Films and Transistors Grown on Sapphire by Metal-Free Chemical Vapor Deposition;Mark A. Fanton,etc;《ACS NANO》;20110911;第5卷(第10期);8062-8069 * |
| Large scale metal-free synthesis of graphene on sapphire and transfer-free device fabrication;Hyun Jae Song,etc;《Nanoscale》;20120329;第4卷(第10期);3050-3054 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541714A (en) * | 2016-06-24 | 2018-01-05 | 北京大学 | A kind of method for fast growing of big size graphene glass |
| CN107541714B (en) * | 2016-06-24 | 2020-02-04 | 北京石墨烯研究院有限公司 | Rapid growth method of large-size graphene glass |
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