CN102674318B - C injection-based Cu film assisted annealing graphene nanoribbon preparation method - Google Patents
C injection-based Cu film assisted annealing graphene nanoribbon preparation method Download PDFInfo
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- CN102674318B CN102674318B CN2012101764992A CN201210176499A CN102674318B CN 102674318 B CN102674318 B CN 102674318B CN 2012101764992 A CN2012101764992 A CN 2012101764992A CN 201210176499 A CN201210176499 A CN 201210176499A CN 102674318 B CN102674318 B CN 102674318B
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Abstract
The invention discloses a C injection-based Cu film assisted annealing graphene nanoribbon preparation method. The preparation method comprises the following implementation steps of: (1) growing a carbide layer on a cleaned Si substrate; (2) growing a 3C-SiC heterogeneous epitaxial thin film at the temperature of 1,200-1,350 DEG C; (3) manufacturing a mask plate consisting of isolation ribbons of100-200 nm and ion injection ribbons of 50-200 nm; (4) injecting C ions into an ion injection region in the 3C-SiC sample wafer; (5) holding the 3C-SiC sample wafer in an epitaxial furnace, heating to 1,200-1,300 DEG C, keeping the constant temperature for 30-90 minutes and pyrolyzing the 3C-SiC of the ion injection ribbon region to generate a carbon film; (6) holding the generated carbon film sample wafer on a Cu film, holding the generated carbon film sample wafer and the Cu film in Ar gas together and annealing at the temperature of 900-1,200 DEG C for 10-20 minutes to generate the graphene nanoribbon. The preparation method has the advantages of simple process, high safety and low 3C-SiC pyrolysis temperature, and the generated graphene nanoribbon has a smooth surface and high continuity and can be used for manufacturing a microelectronic device.
Description
Technical field
The invention belongs to microelectronics technology, relate to a kind of semiconductor film material and preparation method thereof, specifically be based on the Cu film auxiliary annealing graphene nanobelt preparation method that C injects, be used for making microelectronic device.
Technical background
The Micrometer-Nanometer Processing Technology based on silicon materials that with the unicircuit is sign has brought up modern information society.But along with the raising day by day of modern retrofit state of the art, the characteristic dimension of device moves closer in nanometer scale, and operating frequency is more and more higher, and this causes silicon technology to be subjected to the trend of manufacturing process restriction obvious gradually.It is generally acknowledged that the manufacturing limit of silicon materials is 10nm live widths.Because the restriction of quantum size effect, live width just unlikely produces stable electrical properties, product that integrated level is higher less than 10nm.Therefore, be that traditional microelectronic device of core will face unavoidable predicament with silicon, people place hope on the electronics of carbon-based material.
The another kind of carbon-based material that Graphene is had an optimistic view of by people, it not only has the character more more superior than carbon nanotube, has bigger contact resistance but also overcome carbon nanotube, the chirality control that is difficult to go beyond, metal mold is separated with semi-conductor type and many shortcomings such as catalyst impurities, easier to be compatible mutually with the conventional semiconductor Technology, for preparation carbon-based nano device has brought very big handiness, thought that by academia and industry member post-CMOS epoch microelectronics replaces silicon, overcomes the most promising candidate material of technical bottleneck of the more and more littler dimension limit effect that runs into of present electron device.
Graphene has caused extensive concern because its excellent electrology characteristic, and the novel method for preparing Graphene then emerges in an endless stream, but uses maximum two kinds of chemical Vapor deposition process and thermolysis SiC methods that mainly contain.
Chemical Vapor deposition process, it is the most widely used a kind of heavy industrialization method of preparation semiconductor film material, it is to utilize carbon compounds such as methane, ethene as carbon source, by its pyrolytic decomposition growth Graphene at matrix surface, at last with obtaining independently graphene film after the chemical corrosion method removal metal base.The growth of the adjustable Graphenes of parameter such as flow of the type by selecting substrate, the temperature of growth, presoma, as growth velocity, thickness, area etc., the shortcoming of this method is complicated process of preparation, energy consumption is big, cost is higher, accurately controls relatively poorly, and the Graphene lamella that obtains interacts by force with substrate, lost the character of many single-layer graphenes, and the continuity of Graphene not fine.
Thermolysis SiC method is to make by heat the bond rupture of SiC substrate surface carbon silicon to make the lip-deep Si atom distillation of SiC that residue C atom forms Graphene in former substrate surface reconstruct.Yet temperature is higher during the SiC thermolysis, and the Graphene that grows out is island and distributes, and hole is many, and when making device because photoetching, dry etchings etc. can make the electronic mobility of Graphene reduce, thereby have influenced device performance.
Summary of the invention
The objective of the invention is at above-mentioned the deficiencies in the prior art, a kind of Cu film auxiliary annealing graphene nanobelt preparation method who injects based on C is proposed, with the graphene nanobelt of growing selectively, improve graphene nanobelt surface flatness and continuity, avoid simultaneously when postorder is made device, Graphene being carried out the technological process of etching, and the problem that causes electronic mobility to reduce.
For achieving the above object, preparation method of the present invention may further comprise the steps:
(1) the Si substrate base to the 4-12 inch carries out standard cleaning;
(2) the Si substrate base after will cleaning is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank;
(3) at H
2Under the situation of protection reaction chamber is progressively risen to 1000 ℃-1200 ℃ of carbonization temperatures, feeding flow is the C of 30ml/min
3H
8, substrate is carried out carbonization 4-8min, growth one deck carburization zone;
(4) reaction chamber is warming up to 1200 ℃-1350 ℃ rapidly after, feed the C of 30-60min
3H
8And SiH
4, again at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film;
(5) make the mask plate of being formed by isolation strip and ion implantation band, isolation strip width 100-200nm, ion implantation bandwidth 50-200nm;
(6) utilize mask plate that the 3C-SiC print after growing is injected energy in ion implantation band and be 15-45keV, dosage is 5 * 10
14~ 5 * 10
16Cm
-2The C ion;
(7) the 3C-SiC print that will inject behind the C ion is put into epitaxial furnace, regulates that pressure is 0.5 ~ 1 * 10 in the epitaxial furnace
-6Torr, feeding flow velocity in the stove again is the Ar gas of 500-800ml/min, and epitaxial furnace is heated to 1200-1300 ℃, and constant temperature keeps 30-90min, and the 3C-SiC pyrolysis of ion implantation region generates carbon film;
(8) the carbon film print that generates is placed on the Cu film, they together being placed flow velocity is the Ar gas of 20-100ml/min again, be heated to 900-1200 ℃ of annealing 10-20min down, make carbon film reconstitute graphene nanobelt, take away the Cu film at last, obtain the nano material that isolation strip and graphene nanobelt are alternately formed mutually at extension 3C-SiC.
The present invention compared with prior art has following advantage:
The present invention since growth during 3C-SiC earlier on the Si substrate growth one deck carburization zone as transition, and then growth 3C-SiC, thereby the 3C-SiC quality height of growth.
But the present invention since the 3C-SiC heteroepitaxial growth on the Si disk, thereby the growth cost low.
3. the present invention is because the extension one deck 3C-SiC on the Si sample of elder generation, in the ion implantation band of 3C-SiC sample, injected the C ion again, it is identical with the width that needs the making device to inject bandwidth, the width that is graphene nanobelt equates with the width that needs to make device, has avoided when postorder is made device owing to carrying out the problem that etching causes electronic mobility to reduce to Graphene.
4. the present invention anneals at the Cu film owing to utilizing, thereby the easier reconstruct formation of the carbon film that generates continuity is better, ganoid graphene nanobelt.
Description of drawings
Fig. 1 is the schema that the present invention prepares Graphene.
Embodiment
With reference to Fig. 1, making method of the present invention provides following three kinds of embodiment.
Embodiment 1
Step 1: remove the sample surfaces pollutent.
4 inches Si substrate bases are carried out cleaning surfaces handle, namely use NH earlier
4OH+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove ionic contamination.
Step 2: the Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank.
Step 3: growth carburization zone.
At H
2Under the situation of protection reaction chamber temperature is progressively risen to 1000 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30ml/min
3H
8, the time length is 8min, at Si substrate growth one deck carburization zone.
Step 4: at carburization zone growth 3C-SiC epitaxial film.
After reaction chamber is warming up to 1200 ℃ rapidly, feed the SiH that flow is respectively 20ml/min and 40ml/min
4And C
3H
8, the time length is 60min; Then at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film.
Step 5: the width according to device is made the mask plate of alternately being made up of mutually isolation strip and ion implantation band, isolation strip width 100nm, and ion implantation bandwidth 200nm, this ion implantation bandwidth is identical with the width of device.
Step 6: utilize and inject energy in the ion implantation band of mask plate in the good 3C-SiC epitaxial film print of growth and be 15keV, dosage is 5 * 10
14Cm
-2The C ion.
Step 7:3C-SiC pyrolysis generates carbon film.
3C-SiC print behind the injection C ion is put into epitaxial furnace, and pressure is 0.5 * 10 in the epitaxial furnace
-6Torr, and to wherein feeding the Ar gas that flow velocity is 500ml/min, reheat to 1200 ℃, constant temperature keeps 90min, makes the 3C-SiC pyrolysis of ion implantation region generate carbon film.
Step 8: carbon film reconstitutes graphene nanobelt.
(8.1) the carbon film print that generates is taken out from epitaxial furnace, its carbon film is placed on the Cu film of 250nm;
(8.2) carbon film print and Cu film integral body being placed flow velocity is the Ar gas of 20ml/min, is 900 ℃ of annealing 20min down in temperature, and the katalysis by metal Cu makes carbon film reconstitute graphene nanobelt;
(8.3) take away the Cu film at last, obtain the nano material that isolation strip and graphene nanobelt are alternately formed mutually at 3C-SiC.
Embodiment 2
Step 1: remove the sample surfaces pollutent.
8 inches Si substrate bases are carried out cleaning surfaces handle, namely use NH earlier
4OH+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove ionic contamination.
Step 2: the Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank.
Step 3: growth carburization zone.
At H
2Under the situation of protection reaction chamber temperature is progressively risen to 1100 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30ml/min
3H
8, the time length is 6min, at Si substrate growth one deck carburization zone.
Step 4: at carburization zone growth 3C-SiC epitaxial film.
After reaction chamber is warming up to 1300 ℃ rapidly, feed the SiH that flow is respectively 30ml/min and 60ml/min
4And C
3H
8, the time length is 45min; Then at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film.
Step 5: the width according to device is made the mask plate of alternately being made up of mutually isolation strip and ion implantation band, isolation strip width 150nm, and ion implantation bandwidth 100nm, this ion implantation bandwidth is identical with the width of device.
Step 6: utilize that to carry out C in the ion implantation band of mask plate to the 3C-SiC print ion implantation.
Injecting energy in the ion implantation band in the good 3C-SiC epitaxial film print of growth is 30keV, and dosage is 5 * 10
15Cm
-2The C ion;
Step 7: the 3C-SiC pyrolysis generates carbon film.
3C-SiC print behind the injection C ion is put into epitaxial furnace, and pressure is 0.8 * 10 in the epitaxial furnace
-6Torr, and to wherein feeding the Ar gas that flow velocity is 600ml/min, reheat to 1250 ℃, constant temperature keeps 60min, makes the 3C-SiC pyrolysis of ion implantation region generate carbon film.
Step 8: carbon film reconstitutes graphene nanobelt.
The carbon film print that generates is taken out from epitaxial furnace and place on the Cu film of 280nm, they together being placed flow velocity is the Ar gas of 60ml/min again, temperature is 1000 ℃ of annealing 15min down, katalysis by metal Cu makes carbon film reconstitute graphene nanobelt, take away the Cu film at last, obtain the nano material that isolation strip and graphene nanobelt are alternately formed mutually at 3C-SiC.
Embodiment 3
Steps A: 12 inches Si substrate bases are carried out cleaning surfaces handle, namely use NH earlier
4OH+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out the back oven dry, to remove ionic contamination.
Step B: the Si substrate base is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank.
Step C: at H
2Under the situation of protection reaction chamber temperature is progressively risen to 1200 ℃ of carbonization temperatures, feeding flow to reaction chamber then is the C of 30ml/min
3H
8, the time length is 4min, at Si substrate growth one deck carburization zone.
Step D: after reaction chamber is warming up to 1350 ℃ rapidly, feed the SiH that flow is respectively 35ml/min and 70ml/min
4And C
3H
8, the time length is 30min; Then at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film.
Step e: the width according to device is made the mask plate of alternately being made up of mutually isolation strip and ion implantation band, isolation strip width 200nm, and ion implantation bandwidth 50nm, this ion implantation bandwidth is identical with the width of device.
Step F: utilize that the injection energy is 45keV in mask plate ion implantation in the good 3C-SiC epitaxial film print of growth, dosage is 5 * 10
16Cm
-2The C ion.
Step G: the 3C-SiC print that will inject behind the C ion is put into epitaxial furnace, and pressure is 1 * 10 in the epitaxial furnace
-6Torr, and to wherein feeding the Ar gas that flow velocity is 800ml/min, reheat to 1300 ℃, constant temperature keeps 30min, makes the 3C-SiC pyrolysis of ion implantation region generate carbon film.
Step H: the carbon film print that generates is taken out from epitaxial furnace and place on the Cu film of 300nm, they together being placed flow velocity is the Ar gas of 100ml/min again, temperature is 1200 ℃ of annealing 10min down, katalysis by metal Cu makes carbon film reconstitute graphene nanobelt, take away the Cu film at last, obtain the nano material that isolation strip and graphene nanobelt are alternately formed mutually at 3C-SiC.
Claims (4)
1. Cu film auxiliary annealing graphene nanobelt preparation method who injects based on C may further comprise the steps:
(1) the Si substrate base to the 4-12 inch carries out standard cleaning: use NH earlier
4OH+H
2O
2Reagent soaked the Si print 10 minutes, took out the back oven dry, to remove print surface organic residue; Re-use HCl+H
2O
2Reagent soaked print 10 minutes, took out the back oven dry, to remove ionic contamination;
(2) the Si substrate base after will cleaning is put into CVD system response chamber, reaction chamber is vacuumized reach 10
-7The mbar rank;
(3) at H
2Under the situation of protection reaction chamber is progressively risen to 1000 ℃-1200 ℃ of carbonization temperatures, feeding flow is the C of 30ml/min
3H
8, substrate is carried out carbonization 4-8min, growth one deck carburization zone;
(4) reaction chamber is warming up to 1200 ℃-1350 ℃ rapidly after, feed the C of 30-60min
3H
8And SiH
4, again at H
2Protection progressively is cooled to room temperature down, finishes the growth of 3C-SiC epitaxial film;
(5) make the mask plate of being formed by isolation strip and ion implantation band, isolation strip width 100-200nm, ion implantation bandwidth 50-200nm;
(6) utilize mask plate that the 3C-SiC print after growing is injected energy in ion implantation band and be 15-45keV, dosage is 5 * 10
14-5 * 10
16Cm
-2The C ion;
(7) the 3C-SiC print that will inject behind the C ion is put into epitaxial furnace, regulates that pressure is 0.5 * 10 in the epitaxial furnace
-6-1 * 10
-6Torr, feeding flow velocity in the stove again is the Ar gas of 500-800ml/min, and epitaxial furnace is heated to 1200-1300 ℃, and constant temperature keeps 30-90min, and the 3C-SiC pyrolysis of ion implantation region generates carbon film;
(8) the carbon film print that generates is placed on the Cu film, they together being placed flow velocity is the Ar gas of 20-100ml/min again, be heated to 900-1200 ℃ of annealing 10-20min down, make carbon film reconstitute graphene nanobelt, take away the Cu film at last, obtain the nano material that isolation strip and graphene nanobelt are alternately formed mutually at extension 3C-SiC.
2. the Cu film auxiliary annealing graphene nanobelt preparation method who injects based on C according to claim 1 is characterized in that the SiH that described step (4) feeds
4And C
3H
8, its flow is respectively 20-35ml/min and 40-70ml/min.
3. the Cu film auxiliary annealing graphene nanobelt preparation method who injects based on C according to claim 1, it is characterized in that the injection bandwidth in the described step (5) is identical with the width of needs making device, namely the width of graphene nanobelt equates with the width that needs to make device.
4. the Cu film auxiliary annealing graphene nanobelt preparation method who injects based on C according to claim 1 is characterized in that the Cu film thickness in the described step (8) is 250-300nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602503A (en) * | 2009-07-20 | 2009-12-16 | 西安电子科技大学 | The method of 4H-SiC silicon face extending and growing graphene |
| US20110309336A1 (en) * | 2010-06-18 | 2011-12-22 | Samsung Electronics Co., Ltd. | Semiconducting graphene composition, and electrical device including the same |
| CN102433586A (en) * | 2011-10-02 | 2012-05-02 | 西安电子科技大学 | Method for epitaxial growth of wafer-level graphene on 4H/6H-SiC (0001) surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602503A (en) * | 2009-07-20 | 2009-12-16 | 西安电子科技大学 | The method of 4H-SiC silicon face extending and growing graphene |
| US20110309336A1 (en) * | 2010-06-18 | 2011-12-22 | Samsung Electronics Co., Ltd. | Semiconducting graphene composition, and electrical device including the same |
| CN102433586A (en) * | 2011-10-02 | 2012-05-02 | 西安电子科技大学 | Method for epitaxial growth of wafer-level graphene on 4H/6H-SiC (0001) surface |
Non-Patent Citations (2)
| Title |
|---|
| 廖志宇等.石墨烯纳米间隙电极对的制备研究进展.《电子元件与材料》.2011,第30卷(第8期),第72-75页. |
| 石墨烯纳米间隙电极对的制备研究进展;廖志宇等;《电子元件与材料》;20110831;第30卷(第8期);第72-75页 * |
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