KR101563806B1 - Doped graphene pattern manufacturing method and manufacturing method of manufacturing a p-n diode including thereof - Google Patents

Abstract

The present invention provides a method of making a doped graphene pattern. The method includes: spraying a carbon precursor including an n-type carbon precursor on a substrate; forming an amorphous carbon pattern by irradiating the injected carbon precursor with an electron beam or an ion beam; and heat treating the amorphous carbon pattern to heat the n Type graphene pattern. Thereby, it is possible to reduce the substrate damage which occurs when forming the graphene pattern, and to form the graphene pattern without deteriorating the graphene characteristics. Further, a graphene pattern and a p-n diode can be formed through a simple process without a separate photolithography process.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a doped graphene pattern and a manufacturing method of a p-n diode including the manufacturing method,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing graphene, and more particularly, to a method of manufacturing a doped graphene pattern.

Graphene has been actively studied for use as a diode-based material because it can be formed in a large area, has not only electrical, mechanical, and chemical stability but also has high carrier mobility. It is also attracting attention as a next-generation semiconductor material to replace silicon.

Formation of patterned graphene is indispensable for element application of such graphene. In the case of the prior art, mechanical peeling, chemical vapor deposition, or the like for patterning graphene. The graphene is deposited on the substrate through a wet semiconductor process or the like, and the graphene is patterned through a separate photolithography process.

Therefore, there is a problem that a process of several steps is required, a part of the substrate or graphene is damaged in the process, and the impurity penetrates into the graphene, thereby deteriorating the quality of the graphene.

In addition, graphene synthesis has been widely used for graphene synthesis, and p-type graphene has been mostly studied, and n-type doped graphene using n-type dopant has to be synthesized artificially, Can be obtained.

Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a method of manufacturing a doped graphene pattern capable of improving the quality of a graphene pattern and a method of manufacturing a pn diode including the method .

It is another object of the present invention to provide a method of manufacturing a doped graphene pattern capable of forming a graphene pattern through a simple process without a separate photolithography process, and a manufacturing method of a p-n diode including the manufacturing method.

One aspect of the invention provides a method of making a doped graphene pattern.

The method includes: spraying a carbon precursor including an n-type carbon precursor on a substrate; forming an amorphous carbon pattern by irradiating the injected carbon precursor with an electron beam or an ion beam; and heat treating the amorphous carbon pattern to heat the n Type graphene pattern.

The method may further include forming a metal catalyst layer on the amorphous carbon pattern before forming the graphene pattern. The method may further include removing the metal catalyst layer after forming the graphene pattern. have. Preferably, the beam acceleration value of the electron beam or the ion beam is 0.1 keV to 200 keV, and the heat treatment is performed in a vacuum state or a reducing gas atmosphere at 800 ° C to 1200 ° C.

The n-type carbon precursor is _{C 3 H 3 N 3 (1,3,5} -Triazine, 1,2,4-Triazine, 1,2,3-Triazine), C 12 H 8 N 2 (Phenazine), C 4 _{H 10 N 2 (Piperazine),} C 4 H 4 N 2 (Pyrazine, pyrimidine, pyridazine), C 8 H 12 N 2 (2- (2-Methylaminoethyl) pyridine), C 6 H 8 N 2 (4- (Aminomethyl ) pyridine, 2- (Methylamino) pyridine), C ₃ H ₄ N ₄ (3-Amino-1,2,4-triazine), C ₂₄ H ₁₅ N ₃ O ₆ (4,4,4- 2,4,6-triyl-tribenzoic acid), C ₃ N ₃ Na ₃ S ₃ (1,3,5-Triazine-2,4,6-trithiol trisodium), C ₃ H ₂ Cl ₁₂ N ₄ (2- Amino-4,6-dichloro-1,3,5- triazine), and _{C 9 H 18 N 6 (2,4,6} -Tris (dimethylamino) is selected from the group consisting of -1,3,5-triazine) At least one can be used.

Another aspect of the present invention provides a method of manufacturing a p-n diode.

The method includes: spraying a carbon precursor containing an n-type carbon precursor on a substrate; forming an amorphous carbon pattern by irradiating the injected carbon precursor with an electron beam or an ion beam; Forming a graphene pattern; and forming p-type graphene on the n-type graphene pattern to form a pn junction with the n-type graphene pattern.

At this time, the step of forming the p-type graphene may include a step of spraying a carbon precursor containing a p-type carbon precursor on the n-type graphene pattern, Forming a second amorphous carbon pattern by irradiating the carbon precursor with an electron beam or an ion beam, and heat treating the second amorphous carbon pattern to form a p-type graphene pattern, wherein the p-type carbon precursor _{B (C 6 H 5) 3} (Triphenylborane), C 9 H 11 BO 2 (trans-3-phenyl-1-propen-1-ylboronic acid), CH 3 OC 6 H 4 CH = CHB (OH) 2 (trans -2- (4-methoxyphenyl) vinylboronic acid ), C 6 H 5 BC l2 (Dichlorophenylborane), C 6 H 7 BO 2 (benzeneboronic acid), C 6 H 7 BO 3 (3-Hydroxyphenylboronic acid), C 6 H 8 _{B 2 O 4 (Benzene-1,4} -diboronic acid), C 6 H 13 BO 2 (Cyclohexylboronic acid), HCOC 6 H 4 B (OH) 2 (2-Formylphenylboronic acid, 3-Formylphenylboronic acid, 4-formylphenylboronic acid _{,), HO 2 CC 6 H} 4 (OH) ₂ , CH ₃ C ₆ H ₄ B (OH) ₂ , o-tolylboronic acid, m-tolylboronic acid and C ₇ H ₉ BO ₂ (4-methylphenylboronic acid) And may include at least one.

According to the present invention, a method of manufacturing a doped graphene pattern and a manufacturing method of a pn diode including the method of manufacturing the same reduces the damage of a substrate generated when forming a graphene pattern, Can be formed.

In addition, doped graphene patterns and p-n diodes can be formed through a simple process without a separate wet semiconductor process or photolithography process.

1A to 1D are cross-sectional views illustrating a method of manufacturing an n-type graphene pattern according to an embodiment of the present invention.
2A and 2B are cross-sectional views illustrating a method of manufacturing a pn diode according to an embodiment of the present invention.
3 is a top view of a pn diode according to an embodiment of the present invention.
4 is a graph showing Raman peaks before and after the heat treatment in Production Example 1. Fig.
Fig. 5 is a SEM photograph of the preparation example 1 before and after the heat treatment.
6 is a graph showing the resistance change according to the voltage of Production Example 1. Fig.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It is to be understood, however, that the present invention is not limited to the embodiments described herein but may be embodied in other forms and includes all equivalents and alternatives falling within the spirit and scope of the present invention.

When a layer is referred to herein as being "on" another layer or substrate, it may be formed directly on another layer or substrate, or a third layer may be interposed therebetween. In the present specification, directional expressions of the upper side, upper side, upper side, and the like can be understood as meaning lower, lower, lower, and the like according to the standard. That is, the expression of the spatial direction should be understood in the relative direction and should not be construed as limiting in the absolute direction.

In the drawings, the thicknesses of the layers and regions may be exaggerated or omitted for the sake of clarity. Like reference numerals designate like elements throughout the specification.

Fabrication of n-type graphene pattern

FIGS. 1A to 1D are cross-sectional views illustrating a method of manufacturing a doped graphene pattern according to an embodiment of the present invention.

Referring to FIG. 1A, an amorphous carbon pattern 20a is formed using an ion beam or electron beam evaporator. First, the substrate 10 is loaded in a vacuum chamber of the deposition apparatus, and a carbon precursor injecting needle 120 is filled with a carbon precursor containing an n-type carbon precursor and is sprayed onto the substrate 10. Then, an electron beam or an energy beam of the ion beam is applied onto the substrate 10 from the electron or ion gun 100 in a desired shape. At this time, the energy beam can be deflected by the electron lens 110 utilizing the Lorentz force.

Further, the ion beam or the transfer beam can be irradiated while the substrate to be deposited is moved relatively finely.

The injected carbon precursor is irradiated with the ion beam or the electron beam, and the amorphous carbon pattern 20a is selectively formed only at the position irradiated with the ion beam or the electron beam. Therefore, the amorphous carbon pattern 20a having a desired shape can be formed without a separate photolithography process.

The n-type carbon precursor is a hydrocarbon compound of which the n-type graphene After the heat treatment described _{below, C 3 H 3 N 3 (} 1,3,5-Triazine, 1,2,4-Triazine, 1,2,3- Triazine), C ₁₂ H ₈ N ₂ (Phenazine), C ₄ H ₁₀ N ₂ (Piperazine), C ₄ H ₄ N ₂ (Pyrazine, pyrimidine, pyridazine), C ₈ H ₁₂ N ₂ (2- _{) pyridine), C 6 H 8} N 2 (4- (Aminomethyl) pyridine, 2- (Methylamino) pyridine), C 3 H 4 N 4 (3-Amino-1,2,4-triazine), C 24 H 15 N ₃ O ₆ (4,4,4-s-Triazine-2,4,6-triyl-tribenzoic acid), C ₃ N ₃ Na ₃ S ₃ (1,3,5-Triazine- trithiol trisodium), C ₃ H ₂ Cl ₁₂ N ₄ (2-Amino-4,6-dichloro-1,3,5-triazine), and C ₉ H ₁₈ N ₆ (2,4,6- -1,3,5-triazine), but any carbon compound which can be converted into n-type graphene upon heat treatment is all possible.

In addition, the carbon precursor may include a carbon precursor other than the n-type carbon precursor. The general carbon precursor may include, for example, methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ), propane (CH ₃ CH ₂ CH ₃ ) C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), cyclohexane (C ₆ H _12), benzene (C ₆ H _6), toluene (C ₇ H ₈₎ in number, but include at least one selected from the group consisting of, but not limited thereto.

Also, the size or thickness of the amorphous carbon pattern formed according to the energy source type of the electron or ion gun 100 and the beam acceleration value can be adjusted. Generally, as the beam acceleration value is low and the degree of vacuum is low, the size of the pattern to be manufactured is small and thin. On the other hand, as the beam acceleration value is high and the degree of vacuum is high, the size of the pattern to be manufactured is large and thick.

The energy source acceleration value, that is, the beam acceleration value, is preferably 0.1 keV to 200 keV. If the beam acceleration value is less than 0.1 keV, the substance to be deposited may not reach the substrate. If the beam acceleration value exceeds 200 keV, the acceleration of the energy source is high and it may be difficult to form a precise pattern.

The amount of energy irradiation is preferably ¹ mC / cm ² or more.

Referring to FIG. 1B, a metal catalyst layer 30 may be formed on the amorphous carbon pattern 20a.

The metal of the metal catalyst layer 30 may be a material that does not react with the amorphous carbon pattern 20a to form a metal carbide. As such a metal, at least one selected from the group consisting of Ni, Co, Cu, Ru, Ir and Rh can be used.

The metal material may be deposited on the amorphous carbon pattern 20a using a high-vacuum metal evaporator or the like. The metal catalyst layer 30 thus formed helps to form an n-type graphene pattern from the amorphous carbon pattern 20a and contributes to formation of a high quality n-type graphene pattern. However, the step of forming the metal catalyst layer 30 may be omitted.

Referring to FIG. 1C, the amorphous carbon pattern is heat-treated to form an n-type graphene pattern 20b.

At this time, it is preferable that the heat treatment is performed in a vacuum state or a reducing gas atmosphere at 800 ° C to 1200 ° C.

The heat treatment must be performed in a vacuum state or a reducing gas atmosphere so that the n-type graphene pattern 20b can be stably formed. The reducing gas may be a gas atmosphere containing at least one selected from the group consisting of oxygen, nitrogen, hydrogen, helium, and argon. More specifically, it is preferable to perform heat treatment in a vacuum state having a degree of vacuum of 10 ^-3 torr or less. Further, it is preferable that the heat treatment is performed in a state where the carbon source is disconnected.

When the heat treatment temperature is less than 800 ° C, the temperature is low, and it may be difficult to form an n-type graphene pattern from the amorphous carbon pattern. In addition, when the heat treatment temperature exceeds 1200 ° C, the n-type graphene pattern may not be formed uniformly.

The n-type graphene pattern 20b is formed by removing the hydrogen atoms of the carbon precursor and rearranging only the carbon atoms into a two-dimensional hexagonal carbon atom arrangement by heat treatment.

Referring to FIG. 1D, when the metal catalyst layer 30 is formed on the amorphous carbon pattern, the formed metal catalyst layer 30 is removed after the graphene pattern is formed. The metal catalyst layer 30 is etched by using an etchant that can selectively melt only the metal catalyst layer 30. The n-type graphene pattern 20b formed through the heat treatment remains on the substrate 10 from which the metal catalyst layer 30 has been removed.

With this manufacturing method, patterned n-type graphene can be formed without a separate photolithography process, and the process can be simplified. In addition, it is possible to reduce the substrate damage which occurs when forming a graphene pattern, and to form an n-type graphene pattern without deteriorating the n-type graphene characteristics.

Manufacture of p-n junction diode

First, an amorphous carbon pattern is formed from a carbon precursor containing an n-type carbon precursor on the substrate by electron beam or ion beam-induced deposition, and the amorphous carbon pattern is heat-treated to form an n-type graphene pattern. A detailed description of the formation of the n-type graphene pattern will be given with reference to the above description and Figs. 1A to 1D.

2A and 2B are cross-sectional views illustrating a method of manufacturing a p-n diode according to an embodiment of the present invention.

Referring to FIG. 2A, an insulating material 40 may be formed between the n-type graphene patterns 20b or on both sides. However, the present invention is not limited to this, and the step of forming the insulating material 40 may be omitted.

As the insulating material 40, an oxide such as SiO ₂ , Al ₂ O ₃ , or HfO ₂ may be used, but is not limited thereto. The insulating material may be filled by CVD or sputtering.

Referring to FIG. 2B, a p-type graphene pattern 50 is formed on the n-type graphene pattern 20b to form a p-n junction with the n-type graphene pattern 20b.

The method of forming the p-type graphene pattern 50 is not limited to the use of the carbon precursor including the p-type carbon precursor in place of the carbon precursor including the n-type precursor, And is the same as that of the graphene pattern. Specifically, a carbon precursor containing a p-type carbon precursor is sprayed onto the n-type graphene, and an electron beam or an ion beam is irradiated to the injected carbon precursor to form a second amorphous carbon pattern. To form a p-type graphene pattern. The method may further include forming a metal catalyst layer on the amorphous carbon pattern after forming the amorphous carbon pattern. When the metal catalyst layer is formed, the metal catalyst layer may be heat-treated to form a p-type graphene pattern, followed by removing the metal catalyst layer.

However, the p-type carbon precursor is a carbon compound that forms p-type graphene after heat treatment. Examples of the p-type carbon precursor include pB (C ₆ H ₅ ) ₃ (triphenylborane), C ₉ H ₁₁ BO ₂ (trans- _{1-ylboronic acid), CH 3} OC 6 H 4 CH = CHB (OH) 2 (trans-2- (4-methoxyphenyl) vinylboronic acid), C 6 H 5 BC l2 (Dichlorophenylborane), C 6 H 7 BO 2 ( _{benzeneboronic acid), C 6 H 7} BO 3 (3-Hydroxyphenylboronic acid), C 6 H 8 B 2 O 4 (Benzene-1,4-diboronic acid), C 6 H 13 BO 2 (Cyclohexylboronic acid), HCOC 6 H _{4 B (OH) 2 (2} -formylphenylboronic acid, 3-formylphenylboronic acid, 4-formylphenylboronic acid,), HO 2 CC 6 H 4 B (OH) 2 (), CH 3 C 6 H 4 B (OH) 2 ( o-tolylboronic acid, m-tolylboronic acid), and _{C 7 H 9 BO 2 (4} -methylphenylboronic acid) may include at least one selected from the group consisting of, but the heat treatment when the p-type yes possible carbon compounds converted to pin Are all possible.

In addition, the carbon precursor may include a carbon precursor other than the p-type carbon precursor. The general carbon precursor may include, for example, methane (CH ₄ ), ethane (C ₂ H ₆ ), ethylene (C ₂ H ₄ ), acetylene (C ₂ H ₂ ), propane (CH ₃ CH ₂ CH ₃ ) C ₃ H _6), butane (C ₄ H _10), pentane _{(CH 3 (CH 2) 3} CH 3), pentene (C ₅ H _10), dicyclopentadiene (C ₅ H _6), hexane (C ₆ H _14), cyclohexane (C ₆ H _12), benzene (C ₆ H _6), toluene (C ₇ H ₈₎ in number, but include at least one selected from the group consisting of, but not limited thereto.

3 is a top view of a p-n diode according to an embodiment of the present invention. Referring to FIG. 3, the n-type graphene pattern and the p-type graphene pattern may be formed to overlap each other in a ten-sided shape.

The overlapping portion of the n-type graphene pattern layer and the p-type graphene pattern may be a p-n junction (I).

Hereinafter, exemplary embodiments of the present invention will be described in order to facilitate understanding of the present invention. It should be understood, however, that the following examples are intended to aid in the understanding of the present invention and are not intended to limit the scope of the present invention.

≪ Preparation Example 1 > Preparation of graphene pattern >

An electron beam having an acceleration energy of 25 keV and an electron beam energy of 5 mC / cm ² exposed at a unit area was irradiated to the substrate, while a substrate on which an SiO ₂ layer was formed was loaded in a vacuum chamber and a hydrocarbon precursor such as methane was sprayed on the substrate. To form an amorphous carbon pattern. Thereafter, the substrate having the amorphous carbon pattern formed thereon was heat-treated at a temperature of 1000 캜 in an Ar gas atmosphere (50 mTorr) at 100 sccm to form a graphene pattern.

FIG. 4 is a graph showing Raman peaks before and after the heat treatment in Production Example 1, and is a progress of observation using a Raman spectroscopic microscope.

Referring to FIG. 4, Raman spectroscopy near 2570 cm ^-1 is not observed because only amorphous carbon exists before the heat treatment, but after annealing, amorphous carbon is converted to graphene, and Raman spectroscopy near 2570 cm ^-1 is seen have.

As a result, a crystalline graphene pattern is formed from the amorphous carbon pattern through the heat treatment process.

FIG. 5A is a SEM photograph of the sample before the heat treatment in Production Example 1, and FIG. 5B is a SEM photograph after the heat treatment of Production Example 1. FIG.

Referring to FIGS. 5A and 5B, it can be seen that the thickness of the amorphous carbon pattern (FIG. 5A) and the number of unit layers of the graphene pattern (FIG. 5B) are increased by increasing the acceleration value of the electron beam.

6 is a graph showing a change in resistance of a graphene pattern according to Production Example 1 according to a voltage. Specifically, the resistance of the graphene pattern was measured while applying a gate voltage to the Si substrate.

Referring to FIG. 6, it can be seen that the graphene pattern according to the production example exhibits typical graphene electrical properties.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the present invention is not limited to the disclosed exemplary embodiments, and various changes and modifications may be made by those skilled in the art without departing from the scope and spirit of the invention. Change is possible.

10: substrate 20a: amorphous carbon pattern
20b: Graphene pattern 20c: n-type graphene pattern
30: metal catalyst layer 40: insulating material
50: p-type graphene pattern layer I: pn junction
100: electronic gun 110: electron lens
120: Carbon precursor injection needle

Claims (9)

The method comprising: spraying a first carbon precursor containing an n-type carbon precursor on a substrate;
Irradiating the injected first carbon precursor with an electron beam or an ion beam to form a first amorphous carbon pattern;
Annealing the first amorphous carbon pattern to form an n-type graphene pattern; And
Spraying a second carbon precursor containing a p-type carbon precursor on the n-type graphene pattern;
Irradiating the injected second carbon precursor with an electron beam or an ion beam to form a second amorphous carbon pattern; And
And annealing the second amorphous carbon pattern to form a p-type graphene pattern that forms a pn junction with the n-type graphene pattern. The method according to claim 1,
The p-type carbon precursor may be at least one selected from the group consisting of B (C ₆ H ₅ ) ₃ (triphenylborane), C ₉ H ₁₁ BO ₂ (trans-3-phenyl-1-propen-1-ylboronic acid), CH ₃ OC ₆ H ₄ CH═CHB _{(OH) 2 (trans-2-} (4-methoxyphenyl) vinylboronic acid), C 6 H 5 BC l2 (Dichlorophenylborane), C 6 H 7 BO 2 (benzeneboronic acid), C 6 H 7 BO 3 (3-Hydroxyphenylboronic acid ), C ₆ H ₈ B ₂ O ₄ (Benzene-1,4-diboronic acid), C ₆ H ₁₃ BO ₂ (Cyclohexylboronic acid), HCOC ₆ H ₄ B (OH) ₂ (2-Formylphenylboronic acid, acid, 4-formylphenylboronic acid,) , HO 2 CC 6 H 4 B (OH) 2 (), CH 3 C 6 H 4 B (OH) 2 (o-tolylboronic acid, m-tolylboronic acid), and C ₇ H ₉ BO ₂ (4-methylphenylboronic acid). The method according to claim 1,
Forming a first metal catalyst layer on the first amorphous carbon pattern before forming the n-type graphene pattern; And
Further comprising the step of removing the first metal catalyst layer after the step of forming the n-type graphene pattern. The method according to claim 1,
Forming a second metal catalyst layer on the second amorphous carbon pattern before forming the p-type graphene pattern; And
Further comprising the step of removing the second metal catalyst layer after the step of forming the p-type graphene pattern. The method according to claim 1,
Wherein a beam acceleration value of the electron beam or the ion beam is 0.1 keV to 200 keV. The method according to claim 1,
Wherein the heat treatment is performed in a vacuum or a reducing gas atmosphere at a temperature of 800 to 1200 占 폚. The method according to claim 1,
The n-type carbon precursor is _{C 3 H 3 N 3 (1,3,5} -Triazine, 1,2,4-Triazine, 1,2,3-Triazine), C 12 H 8 N 2 (Phenazine), C 4 _{H 10 N 2 (Piperazine),} C 4 H 4 N 2 (Pyrazine, pyrimidine, pyridazine), C 8 H 12 N 2 (2- (2-Methylaminoethyl) pyridine), C 6 H 8 N 2 (4- (Aminomethyl ) pyridine, 2- (Methylamino) pyridine), C ₃ H ₄ N ₄ (3-Amino-1,2,4-triazine), C ₂₄ H ₁₅ N ₃ O ₆ (4,4,4- 2,4,6-triyl-tribenzoic acid), C ₃ N ₃ Na ₃ S ₃ (1,3,5-Triazine-2,4,6-trithiol trisodium), C ₃ H ₂ Cl ₁₂ N ₄ (2- Amino-4,6-dichloro-1,3,5- triazine), and _{C 9 H 18 N 6 (2,4,6} -Tris (dimethylamino) is selected from the group consisting of -1,3,5-triazine) Wherein at least one of the pn junctions is formed. delete delete

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