CN102924120A - Graphical graphene preparation method based on reaction between SiC and chlorine gas and Cu film annealing - Google Patents
Graphical graphene preparation method based on reaction between SiC and chlorine gas and Cu film annealing Download PDFInfo
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- CN102924120A CN102924120A CN2012104845347A CN201210484534A CN102924120A CN 102924120 A CN102924120 A CN 102924120A CN 2012104845347 A CN2012104845347 A CN 2012104845347A CN 201210484534 A CN201210484534 A CN 201210484534A CN 102924120 A CN102924120 A CN 102924120A
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Abstract
The invention discloses a graphical graphene preparation method based on the reaction between SiC and a chlorine gas and the Cu film annealing and mainly solves the problems that the graphene prepared in the prior art can be damaged when serving as a transistor channel material for photoetching process, which results in electron mobility reduction. The manufacturing process comprises the following steps: (1), cleaning an SiC sample; (2), settling SiO2 on the surface of the Sic sample, and curving a graph on the SiO2; (3), allowing the graphical sample to be reacted with Cl2 so as to generate a carbon film; (4), placing the generated carbon film sample into a hydrofluoric acid buffer solution, so as to remove SiO2 outside the graph; (5), coating the Cu film on the SiO2 removed carbon sample through a PVD method, and annealing in an Ar gas so as to allow the graphical graphene to be reconstructed on the carbon film at the graph position; and (6), removing the Cu film on the graphical graphene sample. The method provided by the invention is simple, and is high in safety. The graphene on which the transistor is fabricated can be directly used for a conductive channel without being subjected to photoetching. Therefore, the graphene can be used for producing the graphene transistor with super high mobility.
Description
Technical field
The invention belongs to microelectronics technology, relate to semiconductor film material and preparation method thereof, specifically be based on the Cu film annealing patterned graphene preparation method of SiC and chlorine reaction.
Technical background
Graphene is by sp
2A kind of carbonaceous novel material of the tightly packed one-tenth bi-dimensional cellular of the monolayer carbon atom shape crystalline network of hydridization, this is to find at present the thinnest material.Because its unique two-dirnentional structure and excellent crystallography quality exist abundant and novel physical phenomenon and excellent physicals in the Graphene.Because these good character, Graphene are expected in the acquisition widespread use of the fields such as high-performance nano electron device, matrix material, solar cell, field emmision material, ultracapacitor.Therefore, Graphene becomes rapidly one of focus of Materials science and Condensed Matter Physics field Recent study.Scientific circles think that Graphene very likely replaces silicon and becomes following semiconductor material, has extremely wide application prospect.
Graphene attracts wide attention because its excellent electrology characteristic, and the novel method that then prepares Graphene 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 the carbon compounds such as methane, ethene as carbon source, by its pyrolytic decomposition growing graphene at matrix surface, at last with obtaining independently graphene film after the chemical corrosion method removal metal base.Can regulate and control the growth of Graphene by the type of selecting substrate, the temperature of growth, the parameters such as flow of presoma, such as growth velocity, thickness, area etc., the shortcoming of this method is complicated process of preparation, energy consumption is large, cost is higher, accurately controls relatively poorly, and the graphene sheet layer that obtains interacts by force with substrate, lost the character of many Graphenes, and the continuity of Graphene not fine.
Thermolysis SiC method is by heat so that the bond rupture of SiC substrate surface carbon silicon makes the lip-deep Si atom distillation of SiC, and 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 affected device performance.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the prior art, a kind of Cu film annealing patterned graphene preparation method based on SiC and chlorine reaction is proposed, to realize optionally growing patterned graphene, make the technological process that does not need to carry out etching in the follow-up manufacturing device process, the electronic mobility that guarantees Graphene is stable, improves device performance.
For achieving the above object, preparation method of the present invention may further comprise the steps:
(1) the SiC print is cleaned, to remove surface contaminant;
(2) the SiC print surface after cleaning utilizes plasma enhanced chemical vapor deposition PECVD method, the thick SiO of deposit one deck 0.5-1.0 μ m
2, as mask;
(3) at SiO
2Mask surface is coated with one deck photoresist material, carves the window identical with the substrate shape of the device of required making at mask again, exposes SiC, forms the figure identical with window shape;
(4) patterned print is placed silica tube, be heated to 700-1100 ℃;
(5) in silica tube, pass into Ar gas and Cl
2The mixed gas of gas continues 4-10min, makes Cl
2React with exposed SiC, generate carbon film;
(6) the carbon film print that generates is placed buffered hydrofluoric acid solution, to remove figure SiO in addition
2
(7) removing SiO
2After carbon film on utilize the thick Cu film of PVD method plating one deck 200-300nm;
The print that (8) will be coated with the Cu film places Ar gas, is 900-1200 ℃ of lower annealing 15-25min in temperature, makes carbon film reconstitute patterned graphene in graph position;
The print that (9) will generate patterned graphene places FeCl
3In the solution to remove the Cu film.
The present invention compared with prior art has following advantage:
1. the present invention is owing to anneal at the Cu film, thereby the easier reconstruct of the carbon film that generates forms preferably Graphene of continuity.
2. the present invention is because the patterned graphene of having grown optionally need not that it is carried out photoetching and can directly be used as conducting channel when this Graphene is made transistor, so electronic mobility can not reduce, and the Graphene transistor of producing has the superelevation mobility.
3. the present invention is owing to utilize SiC and Cl
2Solid/liquid/gas reactions, thereby the Graphene smooth surface that generates, voidage is low, and thickness is controlled easily.
4. SiC and Cl among the present invention
2Can under lower temperature and normal pressure, react, and speed of reaction is fast.
5. the method technique of the present invention's use is simple, and save energy is safe.
Description of drawings
Fig. 1 is the device synoptic diagram that the present invention prepares Graphene;
Fig. 2 is the schema that the present invention prepares Graphene.
Embodiment
With reference to Fig. 1, Preparation equipment of the present invention mainly is comprised of silica tube 1 and resistance furnace 2, and wherein silica tube 1 is provided with inlet mouth 3 and air outlet 4, and resistance furnace is 2 for the annular hollow structure, and silica tube 1 is inserted in the resistance furnace 2.
With reference to Fig. 2, making method of the present invention provides following three kinds of embodiment.
Step 1: clean the 6H-SiC print, to remove surface contaminant.
(1.1) the 6H-SiC substrate base is used NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove the sample surfaces organic residue;
(1.2) the 6H-SiC print that will remove behind the surperficial organic residue re-uses HCl+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove ionic contamination.
Step 2: at 6H-SiC print surface deposition one deck SiO
2
(2.1) the 6H-SiC print after will cleaning is put into the PECVD system, and the initialization system internal pressure is 3.0Pa, and radio frequency power is 100W, and temperature is 150 ℃;
(2.2) in system, pass into the SiH that flow velocity is respectively 30sccm, 60sccm and 200sccm
4, N
2O and N
2, the time length is 20min, makes SiH
4And N
2The O reaction is at the thick SiO of 6H-SiC print surface deposition one deck 0.5 μ m
2Mask layer.
Step 3: at SiO
2Carve figure on the layer.
(3.1) at SiO
2Spin coating one deck photoresist material on the layer;
(3.2) make reticle according to making device tpo substrate shape, and then carry out photoetching, figure on the reticle is transferred to SiO
2On the layer;
(3.3) corrode SiO with buffered hydrofluoric acid
2, expose 6H-SiC, form the figure on the reticle.
Step 4: with the patterned print silica tube of packing into, and the exhaust heating.
(4.1) patterned print is put into silica tube 1, silica tube is placed resistance furnace 2;
(4.2) passing into flow velocity from inlet mouth 3 to silica tube is the Ar gas of 80sccm, to silica tube carry out 10 minutes emptying, air 4 is discharged from the air outlet;
(4.3) open the resistance furnace power switch, silica tube is heated to 700 ℃.
Step 5: generate carbon film.
Pass into Ar gas and the Cl that flow velocity is respectively 98sccm and 2sccm to silica tube
2Gas continues 4 minutes, makes Cl
26H-SiC reaction with exposed generates carbon film.
Step 6: remove remaining SiO
2
The carbon film print that generates is taken out and places buffered hydrofluoric acid solution from silica tube, to remove the SiO outside the figure
2, this solution is to be that 1: 10 hydrofluoric acid and water is formulated with ratio.
Step 7: with PVD method plating Cu film.
To remove SiO
2The carbon film print place the PVD coating equipment, it is 6.0 * 10 that vacuum tightness is set
-4Pa, direct current DC sputtering power is 300W, and operating pressure is 1.1Pa, and the Ar gas velocity is 60ml/min, and sputtering time is 10min, forms the thick Cu film of one deck 200nm at the carbon film print.
Step 8: reconstitute patterned graphene.
The print that is coated with the Cu film is placed the Ar gas of 80sccm, is 900 ℃ of lower annealing 25 minutes in temperature, makes carbon film reconstitute patterned graphene in graph position.
Step 9: remove the Cu film.
The print of the patterned graphene that generates is placed FeCl
3To remove the Cu film, obtain the patterned graphene material in the solution.
Step 1: clean the 4H-SiC print, to remove surface contaminant.
The 4H-SiC substrate base is used first NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove ionic contamination.
Step 2: at 4H-SiC print surface deposition one deck SiO
2
4H-SiC print after cleaning is put into the PECVD system, and internal system pressure is set to 3.0Pa, and radio frequency power is 100W, and temperature is 150 ℃; In system, pass into the SiH that flow velocity is respectively 30sccm, 60sccm and 200sccm
4, N
2O and N
2, the time length is 75min, makes SiH
4And N
2The O reaction is at the thick SiO of 4H-SiC print surface deposition one deck 0.8 μ m
2
Step 3: at SiO
2Carve figure on the layer.
First at SiO
2Spin coating one deck photoresist material on the layer is made reticle according to making device widths; And then carry out photoetching, figure on the reticle is transferred to SiO
2On the layer; Corrode SiO with buffered hydrofluoric acid
2, expose 4H-SiC, form the figure on the reticle.
Step 4: with the patterned print silica tube of packing into, and the exhaust heating.
Patterned print is placed silica tube 1, silica tube is placed resistance furnace 2; Passing into flow velocity from inlet mouth 3 to silica tube is the Ar gas of 80sccm, to silica tube carry out 10 minutes emptying, air 4 is discharged from the air outlet; Open again the resistance furnace power switch, silica tube is heated to 1000 ℃.
Step 5: generate carbon film.
Pass into Ar gas and the Cl that flow velocity is respectively 97sccm and 3sccm to silica tube
2Gas continues 5 minutes, makes Cl
24H-SiC reaction with exposed generates carbon film.
Step 6: identical with the step 6 of embodiment 1.
Step 7: with PVD method plating Cu film.
To remove SiO
2The carbon film print place the PVD coating equipment, it is 6.0 * 10 that vacuum tightness is set
-4Pa, direct current DC sputtering power is 300W, and operating pressure is 1.1Pa, and Ar gas velocity 60ml/min, sputtering time are 12min, form the thick Cu film of one deck 250nm at the carbon film print.
Step 8: reconstitute patterned graphene.
The print that is coated with the Cu film is placed the Ar gas of 55sccm, is 1000 ℃ of lower annealing 20 minutes in temperature, makes carbon film reconstitute patterned graphene in graph position.
Step 9: remove the Cu film.
The print of the patterned graphene that generates is placed FeCl
3To remove the Cu film, obtain the patterned graphene material in the solution.
Steps A: the 6H-SiC substrate base is carried out cleaning surfaces process, namely use first NH
4OH+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove the sample surfaces organic residue; Re-use HCl+H
2O
2Reagent soaked sample 10 minutes, took out post-drying, to remove ionic contamination.
Step B: the 6H-SiC print after will cleaning is put into the PECVD system, and internal system pressure is set to 3.0Pa, and radio frequency power is 100W, and temperature is 150 ℃; In system, pass into the SiH that flow velocity is respectively 30sccm, 60sccm and 200sccm
4, N
2O and N
2, continue 100min, make SiH
4And N
2The O reaction is at the thick SiO of 6H-SiC print surface deposition one deck 1.0 μ m
2
Step C: identical with the step 3 of embodiment 1.
Step D: patterned print is placed silica tube 1, and silica tube is placed resistance furnace 2; Passing into flow velocity from inlet mouth 3 to silica tube is the Ar gas of 80sccm, to silica tube carry out 10 minutes emptying, air 4 is discharged from the air outlet; Open again the resistance furnace power switch, silica tube is heated to 1100 ℃.
Step e: in silica tube, pass into Ar gas and the Cl that flow velocity is respectively 95sccm and 5sccm
2Gas continues 10 minutes, makes Cl
26H-SiC reaction with exposed generates carbon film.
Step F: identical with the step 6 of embodiment 1.
Step G: will remove SiO
2The carbon film print place the PVD coating equipment, it is 6.0 * 10 that vacuum tightness is set
-4Pa, direct current DC sputtering power is 300W, and operating pressure is 1.1Pa, and the Ar gas velocity is 60ml/min, and sputtering time is 15min, forms the thick Cu film of one deck 300nm at the carbon film print.
Step H: the print that will be coated with the Cu film places the Ar gas of 30sccm, is 1200 ℃ of lower annealing 15 minutes in temperature, makes carbon film reconstitute patterned graphene in graph position.
Step I: remove the Cu film.
The print of the patterned graphene that generates is placed FeCl
3To remove the Cu film, obtain the patterned graphene material in the solution.
Claims (8)
1. one kind based on the Cu film of SiC and chlorine reaction annealing patterned graphene preparation method, may further comprise the steps:
(1) the SiC print is cleaned, to remove surface contaminant;
(2) the SiC print surface after cleaning utilizes plasma enhanced chemical vapor deposition PECVD method, the thick SiO of deposit one deck 0.5-1.0 μ m
2, as mask;
(3) at SiO
2Mask surface is coated with one deck photoresist material, carves the window identical with the substrate shape of the device of required making at mask again, exposes SiC, forms the figure identical with window shape;
(4) patterned print is placed silica tube, be heated to 700-1100 ℃;
(5) in silica tube, pass into Ar gas and Cl
2The mixed gas of gas continues 4-10min, makes Cl
2React with exposed SiC, generate carbon film;
(6) the carbon film print that generates is placed buffered hydrofluoric acid solution, to remove figure SiO in addition
2
(7) removing SiO
2After carbon film on utilize the thick Cu film of PVD method plating one deck 200-300nm;
The print that (8) will be coated with the Cu film places Ar gas, is 900-1200 ℃ of lower annealing 15-25min in temperature, makes carbon film reconstitute patterned graphene in graph position;
The print that (9) will generate patterned graphene places FeCl
3In the solution to remove the Cu film.
2. the method for preparing patterned graphene based on SiC and the chlorine reaction of Cu film annealing according to claim 1 is characterized in that described step (1) cleans the SiC print, is to use first NH
4OH+H
2O
2Reagent soaked the SiC print 10 minutes, took out post-drying, to remove print surface organic residue; Re-use HCl+H
2O
2Reagent soaked print 10 minutes, took out post-drying, to remove ionic contamination.
3. the method for preparing patterned graphene based on SiC and the chlorine reaction of the annealing of Cu film according to claim 1 is characterized in that utilizing in the described step (2) PECVD deposit SiO
2, its processing condition are: SiH
4, N
2O and N
2Flow velocity is respectively 30sccm, 60sccm and 200sccm, and cavity pressure is 3.0Pa, and radio frequency power is 100W, and deposition temperature is 150 ℃, and deposition time is 20-100min.
4. the method for preparing patterned graphene based on SiC and the chlorine reaction of the annealing of Cu film according to claim 1 is characterized in that Ar gas and Cl that described step (5) passes into
2Gas, its flow velocity is respectively 95-98sccm and 5-2sccm.
5. SiC and the method that chlorine reaction prepares patterned graphene based on Cu film annealing according to claim 1 is characterized in that the middle buffered hydrofluoric acid solution of described step (6), are to be that 1: 10 hydrofluoric acid and water is formulated with ratio.
6. the method for preparing patterned graphene based on SiC and the chlorine reaction of the annealing of Cu film according to claim 1 is characterized in that utilizing in the described step (7) PVD plating Cu, and its processing condition are:
Vacuum tightness is 6.0 * 10 in the PVD coating equipment
-4Pa,
Direct current DC sputtering power is 300W,
Operating pressure is 1.1Pa,
The Ar gas velocity is 60ml/min,
Sputtering time is 10-15min.
7. the method for preparing patterned graphene based on SiC and the chlorine reaction of the annealing of Cu film according to claim 1 is characterized in that the flow velocity of Ar gas when described step (8) is annealed is 30-80sccm.
8. the method for preparing patterned graphene based on SiC and the chlorine reaction of the annealing of Cu film according to claim 1 is characterized in that described SiC print, adopts 4H-SiC or 6H-SiC crystal formation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109216153A (en) * | 2017-07-03 | 2019-01-15 | 无锡华润上华科技有限公司 | Improve the method for silicon nitride corrosion resistance and the preparation method of semiconductor devices |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674332A (en) * | 2012-05-23 | 2012-09-19 | 西安电子科技大学 | Method for preparing structured graphene by reaction of SiC and Cl2 based on Cu film annealing |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674332A (en) * | 2012-05-23 | 2012-09-19 | 西安电子科技大学 | Method for preparing structured graphene by reaction of SiC and Cl2 based on Cu film annealing |
Non-Patent Citations (1)
| Title |
|---|
| 大连工学院无机化学教研室: "《无机化学》", 31 March 1978, 人民教育出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109216153A (en) * | 2017-07-03 | 2019-01-15 | 无锡华润上华科技有限公司 | Improve the method for silicon nitride corrosion resistance and the preparation method of semiconductor devices |
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Application publication date: 20130213 |