CN110148557B - Preparation method of PN junction based on carbon-based material - Google Patents
Preparation method of PN junction based on carbon-based material Download PDFInfo
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- CN110148557B CN110148557B CN201910418506.7A CN201910418506A CN110148557B CN 110148557 B CN110148557 B CN 110148557B CN 201910418506 A CN201910418506 A CN 201910418506A CN 110148557 B CN110148557 B CN 110148557B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 229910021389 graphene Inorganic materials 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 9
- 230000002209 hydrophobic effect Effects 0.000 claims description 9
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 239000000725 suspension Substances 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000010586 diagram Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 238000000643 oven drying Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/0405—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising semiconducting carbon, e.g. diamond, diamond-like carbon
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Abstract
The invention belongs to the technical field of semiconductors, and particularly relates to a preparation method of a PN junction based on a carbon-based material. The method does not need to carry out the traditional PN junction doping treatment in the preparation process, has simple preparation process and easy operation, realizes the simple and convenient preparation method of the PN junction under the non-doping process, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a preparation method of a PN junction based on a carbon-based material.
Background
The first Si PN junction was fabricated by bell labs 1940 and the theory of P-N junctions and P-N junction transistors in semiconductors published by william shackley 1948 in the inner publication of bell labs 1948.
PN junctions are the foundation upon which various semiconductor devices are built. According to the difference of the material, doping distribution, geometric structure and bias condition of the PN junction, the device can have the functions of rectifying, promoting photocatalysis, photoluminescence, photosensitivity and the like. Wherein, according to different dopants, a P type or N type semiconductor can be formed, thereby preparing a PN junction. Graphene and related Materials can be tailored to P-type or N-type semiconductors (Journal of Materials Chemistry a, 2018, 6) depending on the nature of the dopant, such as Graphene Oxide (GO) or reduced graphene oxide (rgo) have been widely used as carriers for various semiconductor and metal nanoparticles (ACS Applied Materials & Interfaces 9(5),2017, 4558-4569).
At present, a PN junction is formed by an all-carbon material based on graphene (Nature communications 9, 2018 and 3750), but the preparation method is slightly complicated. Therefore, how to simply prepare the PN junction on the basis of non-doping needs to be solved.
Disclosure of Invention
The invention aims to provide a preparation method of a PN junction based on a carbon-based material, which can realize simple preparation of the PN junction based on the carbon-based material on the non-doping basis.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a PN junction based on a carbon-based material, which comprises the following steps:
carrying out thermal reduction on the carbon-based material to obtain a reduced carbon-based material;
and covering the surface of the reduced carbon-based material with a carbon-based material to obtain the PN junction.
Preferably, the carbon-based material is a graphene oxide film, a partially reduced graphene oxide film, or a graphene film.
Preferably, the film thickness of the carbon-based material is 0.2-100 μm.
Preferably, the preparation method of the carbon-based material comprises the following steps: coating the carbon-based suspension on the surface of hydrophobic paper, and drying to obtain a carbon-based material; the carbon-based suspension is graphene oxide suspension, partially reduced graphene oxide suspension or graphene suspension.
Preferably, the mass concentration of the carbon-based suspension is 0.1-10 mg/mL.
Preferably, the solvent of the carbon-based suspension is one or more of water, ethanol, acetone and dimethyl sulfoxide.
Preferably, the drying temperature is 60-80 ℃, and the drying time is 6-10 h.
Preferably, the temperature of the thermal reduction is 160-200 ℃, and the time of the thermal reduction is 1-6 h.
Preferably, after the thermal reduction is completed, the obtained material is cooled to obtain a reduced carbon-based material; the cooling mode is natural cooling.
Preferably, the covering is performed by applying a carbon-based suspension to the surface of the reduced carbon-based material.
The invention provides a preparation method of a PN junction based on a carbon-based material, which does not need the traditional PN junction doping treatment in the preparation process, has simple preparation process and easy operation, realizes the simple and convenient preparation method of the PN junction under the non-doping process and has good application prospect.
Drawings
Fig. 1 is a diagram of a graphene oxide film prepared in example 1 of the present invention;
FIG. 2 is a diagram showing a reduced carbon-based material prepared in example 1 of the present invention;
FIG. 3 is a diagram of a PN junction composite membrane prepared in example 1 of the present invention and a model thereof; wherein A is the graphene oxide membrane surface of the PN junction composite membrane, B is the reduced carbon base material surface of the PN junction composite membrane, and C is a model diagram of the PN junction composite membrane;
FIG. 4 is an XPS plot of a graphene oxide film prepared according to example 1 of the present invention;
fig. 5 is an I-V curve diagram of the PN junction composite film prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a PN junction based on a carbon-based material, which comprises the following steps:
carrying out thermal reduction on the carbon-based material to obtain a reduced carbon-based material;
and covering the surface of the reduced carbon-based material with a carbon-based material to obtain the PN junction.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention carries out thermal reduction on the carbon-based material to obtain the reduced carbon-based material. In the present invention, the carbon-based material is preferably a graphene oxide film, a partially reduced graphene oxide film, or a graphene film; the film thickness of the carbon-based material is preferably 0.2-100 μm, and more preferably 25 μm. In the invention, the surface flatness, thickness and surface area of the carbon-based material do not influence the performance of the PN junction, and the thickness of the material is limited to ensure that the resistance value of the material is in the detection range of an instrument when the resistance performance of the material is measured, so that the resistance performance detection is realized.
In the present invention, the method for preparing the carbon-based material preferably includes the steps of: coating the carbon-based suspension on the surface of hydrophobic paper, and drying to obtain a carbon-based material; the carbon-based suspension is preferably a graphene oxide suspension, a partially reduced graphene oxide suspension or a graphene suspension, and more preferably a graphene oxide suspension prepared by a modified Hummers method. In the invention, the solvent of the carbon-based suspension is preferably one or more of water, ethanol, acetone and dimethyl sulfoxide; the mass concentration of the carbon-based suspension is preferably the mass concentration conventionally used in the field, more preferably 0.1-10 mg/mL, and even more preferably 5 mg/mL. The coating method is not particularly limited, and may be any coating method known to those skilled in the art, and in the embodiment of the present invention, the coating method is specifically droplet coating. The hydrophobic paper is not particularly limited in the present invention, and hydrophobic paper from sources well known to those skilled in the art, specifically commercially available hydrophobic paper, may be selected. In the invention, the carbon-based material can be stored for a long time in a drying oven at the normal temperature and the normal pressure and at the temperature of-100 ℃ or in other environments without damaging the structure of the carbon-based material film.
The operation and conditions of the drying are not particularly limited, and a drying mode which does not damage the properties of the film and is well known by the technical personnel in the field is selected, the drying method is preferably normal-temperature drying, oven drying, low-temperature freeze drying or vacuum drying, more preferably oven drying, the temperature of the oven drying is preferably 60-80 ℃, more preferably 70 ℃, and the time of the oven drying is preferably 6-10 hours, more preferably 8 hours. The method removes the solvent through a drying process to obtain the carbon-based material.
In the invention, the temperature of the thermal reduction is preferably 160-200 ℃, and more preferably 180 ℃; the time of the thermal reduction is preferably 1-6 h, and more preferably 4 h. The invention controls the temperature of the thermal reduction so that the carbon-based material is partially reduced. According to the invention, the structure of the carbon-based material can be changed by carrying out thermal reduction on the carbon-based material, so that the carbon-based material is partially reduced to obtain the reduced carbon-based material.
After the thermal reduction is completed, the present invention preferably cools the resulting material to obtain a reduced carbon-based material. The cooling conditions are not particularly limited, and the cooling conditions known to those skilled in the art are selected, so that the structure of the material is not damaged; in the embodiment of the present invention, natural cooling is specifically performed. In the invention, the conventional PN doping treatment is not required in the process of preparing the carbon-based material.
After the reduced carbon-based material is obtained, the surface of the reduced carbon-based material is covered with the carbon-based material to obtain the PN junction. In the present invention, the carbon-based material covered is preferably identical to the carbon-based material subjected to thermal reduction. In the present invention, the process of covering is preferably to coat the carbon-based suspension on the surface of the reduced carbon-based material. The coating method is not particularly limited in the present invention, and a method known to those skilled in the art may be selected, and in the embodiment of the present invention, a dispensing method is specifically used. After the covering is completed, the obtained material is dried to obtain the PN junction. The operation and conditions of the drying are not particularly limited, and a drying mode which does not damage the properties of the film and is well known by the technical personnel in the field is selected, the drying method is preferably normal-temperature drying, oven drying, low-temperature freeze drying or vacuum drying, more preferably oven drying, the temperature of the oven drying is preferably 60-80 ℃, more preferably 70 ℃, and the time of the oven drying is preferably 6-10 hours, more preferably 8 hours. In the drying process, on one hand, the solvent can be removed, on the other hand, part of the carbon-based suspension can penetrate into the reduced carbon-based material in the drying process, and after the solvent is dried, the two layers of carbon-based materials can be subjected to self-assembly to obtain the PN junction.
The method for preparing a PN junction based on a carbon-based material according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dripping 1mL of graphene oxide aqueous suspension with the mass concentration of 5mg/mL on the surface of smooth hydrophobic paper, and drying in an oven at 70 ℃ for 8h to obtain a graphene oxide film;
placing the graphene oxide film into an oven at 180 ℃ for thermal reduction for 4 hours, and then naturally cooling at normal temperature to obtain a reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process;
dripping 1mL of graphene oxide aqueous suspension with the mass concentration of 5mg/mL on the surface of the reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process, and the obtained material is put into an oven at 70 ℃ for drying for 8 hours to obtain the non-doped carbon-based material PN junction composite film.
Fig. 1 is a physical diagram of a graphene oxide film prepared in example 1; FIG. 2 is a pictorial view of a reduced carbon-based material prepared in example 1; FIG. 3 is a diagram of a PN junction composite membrane prepared in example 1 and a model thereof; the graphene oxide film surface of the PN junction composite film, (B) the reduced carbon material surface of the PN junction composite film, and (C) the model diagram of the PN junction composite film;
as can be seen from fig. 1 to 3, after the high-temperature thermal reduction, the carbon-based material is subjected to a reduction change, and the reduced carbon-based material has metallic luster, and is not subjected to the conventional PN junction doping treatment, so that an undoped carbon-based material is obtained.
1) The graphene oxide film was subjected to XPS test, and the test results are shown in fig. 4. As can be seen from fig. 4, the content of the O element in the graphene oxide film was 24.51%, the content of the C element was 75.49%, and the content of the other elements was not detected. This illustrates that the graphene oxide film prepared in example 1 of the present invention is an undoped carbon-based material.
2) A Keithley2636B source table SMU instrument is used for testing a current-voltage change curve of the PN junction composite film prepared in example 1 under the condition of-0.5V, and the test result is shown in figure 5. As can be seen from fig. 5, there is a large difference in current through the composite membrane when opposing voltages are applied across the composite membrane A, B. This indicates that there is a significant PN junction between the composite films.
Example 2
Dripping 1mL of graphene oxide aqueous solution with the mass concentration of 6mg/mL on the surface of smooth hydrophobic paper, and drying in an oven at 70 ℃ for 8h to obtain a graphene oxide film;
placing the graphene oxide film into an oven at 180 ℃ for thermal reduction for 6 hours, and then naturally cooling at normal temperature to obtain a reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process;
dripping 1mL of graphene oxide aqueous solution with the mass concentration of 6mg/mL on the surface of the reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process, and the obtained material is put into an oven at 70 ℃ for drying for 8 hours to obtain the non-doped carbon-based material PN junction composite film.
Example 3
Dripping 1mL of graphene oxide aqueous solution with the mass concentration of 8mg/mL on the surface of smooth hydrophobic paper, and drying in an oven at 70 ℃ for 8h to obtain a graphene oxide film;
placing the graphene oxide film into an oven at 180 ℃ for thermal reduction for 2h, and then naturally cooling at normal temperature to obtain a reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process;
dripping 1mL of graphene oxide aqueous solution with the mass concentration of 8mg/mL on the surface of the reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process, and the obtained material is put into an oven at 70 ℃ for drying for 8 hours to obtain the non-doped carbon-based material PN junction composite film.
According to the method of the embodiment 1, the characterization and test results of the embodiments 2 to 3 show that obvious PN junctions also exist between the composite films prepared in the embodiments 2 to 3.
The embodiment shows that the preparation method of the PN junction based on the carbon-based material does not need the traditional doping treatment of the PN junction in the preparation process, is simple in preparation process and easy to operate, realizes the simple preparation method of the PN junction under the non-doping process, and has good application prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A preparation method of a PN junction based on a carbon-based material is characterized by comprising the following steps:
dripping 1mL of graphene oxide aqueous suspension with the mass concentration of 5mg/mL on the surface of smooth hydrophobic paper, and drying in an oven at 70 ℃ for 8h to obtain a graphene oxide film;
placing the graphene oxide film into an oven at 180 ℃ for thermal reduction for 4 hours, and then naturally cooling at normal temperature to obtain a reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process;
dripping 1mL of graphene oxide aqueous suspension with the mass concentration of 5mg/mL on the surface of the reduced carbon-based material; the traditional PN doping treatment is not carried out in the preparation process, and the obtained material is put into an oven at 70 ℃ for drying for 8 hours to obtain the non-doped carbon-based material PN junction composite film.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290477A (en) * | 2011-09-13 | 2011-12-21 | 青岛科技大学 | Photovoltaic cell based on graphene PN junction and preparation method thereof |
| CN107454894A (en) * | 2015-03-23 | 2017-12-08 | 纳米基盘柔软电子素子研究团 | Graphene laminated product and preparation method thereof |
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| KR20140116577A (en) * | 2013-03-25 | 2014-10-06 | 인텔렉추얼디스커버리 주식회사 | Light generating device and method of manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102290477A (en) * | 2011-09-13 | 2011-12-21 | 青岛科技大学 | Photovoltaic cell based on graphene PN junction and preparation method thereof |
| CN107454894A (en) * | 2015-03-23 | 2017-12-08 | 纳米基盘柔软电子素子研究团 | Graphene laminated product and preparation method thereof |
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