KR20130114470A - Method for transfering graphene films and device using the same - Google Patents

Method for transfering graphene films and device using the same Download PDF

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Publication number
KR20130114470A
KR20130114470A KR1020120036884A KR20120036884A KR20130114470A KR 20130114470 A KR20130114470 A KR 20130114470A KR 1020120036884 A KR1020120036884 A KR 1020120036884A KR 20120036884 A KR20120036884 A KR 20120036884A KR 20130114470 A KR20130114470 A KR 20130114470A
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South Korea
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thin film
graphene
graphene thin
support
pss
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KR1020120036884A
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Korean (ko)
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이광희
강영호
이종훈
이병훈
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광주과학기술원
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Priority to KR1020120036884A priority Critical patent/KR20130114470A/en
Priority to PCT/KR2012/010337 priority patent/WO2013154248A1/en
Publication of KR20130114470A publication Critical patent/KR20130114470A/en

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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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
    • H01L21/2007—Bonding of semiconductor wafers to insulating substrates or to semiconducting substrates using an intermediate insulating layer
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/68—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for positioning, orientation or alignment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0016—Processes relating to electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40—Materials therefor

Abstract

Disclosed are a graphene thin film transfer method and a device using the same. Graphene thin film transfer method according to an embodiment of the present invention comprises a first step of attaching a support thin film to the graphene thin film formed on the substrate; A second step of removing the substrate; And a third step of manufacturing a device including the support thin film to which the graphene thin film is attached as a functional layer.

Description

Graphene thin film transfer method and device using the same {METHOD FOR TRANSFERING GRAPHENE FILMS AND DEVICE USING THE SAME}

The present invention relates to a graphene thin film transfer method and a device using the same.

Low-level nanomaterials composed of carbon atoms include fullerene, carbon nanotubes, graphene, and graphite. Among nanomaterials composed of such carbon atoms, graphene, in particular, has attracted much attention recently because its electrical, mechanical, and chemical properties are very stable and can be used in various electronic devices.

Since the graphene thin film having the graphene thin film is synthesized in a large area through a wafer base or a metal base, a transfer process for transferring the synthesized graphene thin film to a desired position is required for application to an electronic device or an electronic device. . In this regard, Figure 1 schematically shows a conventional graphene thin film transfer method.

Referring to FIG. 1, in the graphene thin film transfer method, the graphene thin film 2 is first formed on the substrate 1 (FIG. 1A). Next, the support thin film 3 is attached on the graphene thin film 2. The support thin film 3 is for preventing the graphene thin film 3 from being damaged during the transfer of the graphene thin film 2, and a PMMA (polymethyl methacrylate) thin film or a heat-peelable tape is generally used. (FIG. 1B). Next, after the substrate 1 is removed by etching or the like (FIG. 1C), the graphene thin film 2 attached to the support thin film 3 is transferred to a desired position of the electronic device (or electronic device). 1 illustrates a case where the graphene electrode is transferred onto the transparent substrate 4 as an example. Finally, the transfer of the graphene thin film 2 is completed by removing the support thin film 3 (FIG. 1D).

However, the above-described conventional graphene thin film transfer method has the following problems.

First, due to the reactive solution used in the process of removing the support thin film 3, the characteristics of the electronic device (electronic device) can be reduced. For example, in the case of using the PMMA as the support thin film 3, in order to remove the support thin film 3, a strong reactive solution such as acetone must be used. There is a risk of deteriorating the characteristics. In addition, even when a heat-peelable tape is used as the support thin film 3, a heat treatment process is required in the process of removing the support thin film 3, so that the characteristics of the entire device may be degraded during the heat treatment process.

Second, even after the support thin film 3 is removed, the residues r of the support thin film 3 remain in the graphene thin film 2, thereby degrading the performance of the entire device. For example, in the case of a non-conductive support thin film such as PMMA, residues remaining on the graphene thin film 2 increase the contact resistance of the graphene thin film 2, which may reduce device performance.

The problems described above act as obstacles in applying the graphene thin film to organic devices, flexible materials, etc., which are sensitive to physical and chemical treatments, and the solution is being sought.

In the embodiments of the present invention to provide a graphene thin film transfer method that does not require a support thin film removal process by including a support thin film with a graphene thin film as a functional layer of the device.

In addition, to provide an electronic device manufactured by including the graphene thin film transfer method.

According to an aspect of the invention, the first step of attaching a support thin film to the graphene thin film formed on the substrate; A second step of removing the substrate; And a third step of fabricating a device including the support thin film to which the graphene thin film is attached as a functional layer.

At this time, the graphene thin film may be formed by chemical vapor deposition.

Meanwhile, the support thin film may be made of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonate).

At this time, between the first step and the second step, may further comprise the step of immersing the substrate, the graphene thin film and the support thin film laminated in a polar solution.

At this time, the polar solution is ethylene glycol, dimethyl sulfoxide (DMSO), glycerol, N, N- dimethyl formamide (DMF), sorbitol, N-methyl pyrrolidone (NMP), nitromethane, acetonitrile and methanol It may be at least one solution selected from the group consisting of.

On the other hand, the support thin film is made of an organic polymer material, the organic polymer material is polyaniline-based, polypyrrole-based, polyacetylene-based, polyethylenedioxylthiophene-based, polyphenylenevinylene-based, polyfluorene-based, polyparaphenylene-based It may be a material doped with one or more selected from the group consisting of, polyalkylthiophene-based and polypyridine-based.

In addition, the support thin film is made of a metal oxide material, the metal oxide material is titanium (Ti), zinc (Zn), strontium (Sr), indium (In), barium (Ba), potassium (K), niobium ( Nb), iron (Fe), tantalum (Ta), tungsten (W), bismuth (Bi), nickel (Ni), copper (Cu), molybdenum (Mo), cerium (Ce), platinum (Pt), silver ( Ag), rhodium (Rh) and ruthenium (Ru) can be formed from one or more metal alkoxides.

Meanwhile, the device of the third step may be a light emitting device, an optoelectronic device, a thin film transistor, or an energy storage device.

According to another aspect of the present invention, an electronic device manufactured by including the graphene thin film transfer method according to an aspect of the present invention may be provided.

In the embodiments of the present invention by including a support thin film with a graphene thin film as a functional layer of the device to eliminate the need to remove the support thin film, it is possible to prevent device characteristics and performance degradation due to the support thin film removal process. .

In addition, it is possible to prevent deterioration of device characteristics due to residues remaining on the graphene after removing the supporting thin film.

In addition, since the electronic device can be manufactured without removing the supporting thin film, the manufacturing process of the electronic device can be simplified.

In addition, when the PEDOT: PSS support thin film is used, the conductivity of the PEDOT: PSS support thin film is increased due to the increased doping during graphene transfer, thereby improving device characteristics.

1 is a view schematically showing a conventional graphene thin film transfer method.
2 is a view schematically showing a graphene thin film transfer method according to an embodiment of the present invention.
3 is a graph showing the sheet resistance measurement results of Comparative Examples and Examples.
4 is a graph showing the results of measuring the transmittance of the Comparative Example and Example.
5A to 5C are photographs of morphologies and currents of Comparative Examples 1 and 2 and Examples.
6 is a graph showing the surface roughness and the current measurement results of Comparative Examples 1,2 and Examples.
7 is a graph illustrating IV curves and PCE measurement results of a first organic solar cell.
8 is a graph illustrating IV curves and PCE measurement results of a second organic solar cell.
9 is a graph comparing light absorption rates before and after iron chloride treatment.
10 is an IV curve graph with and without iron chloride treatment.

Hereinafter, embodiments of the present invention will be described in detail.

2 is a view schematically showing a graphene thin film transfer method (hereinafter, graphene thin film transfer method) according to an embodiment of the present invention.

Referring to FIG. 2, the graphene thin film transfer method may include a first step of attaching the support thin film 30 to the graphene thin film 20 formed on the substrate 10; A second step of removing the substrate (10); And a third step of manufacturing a device including the support thin film 30 to which the graphene thin film 20 is attached as a functional layer.

Hereinafter, each step will be described in detail.

1. The first step

The support thin film 30 is attached to the graphene thin film 20 formed on the substrate 10 (see FIGS. 2A and 2B).

The substrate 10 corresponds to a base material for forming the graphene thin film 20, and the material of the substrate 10 is not particularly limited. For example, the substrate 10 may include silicon (Si), nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), aluminum (Al), chromium (Cr), copper (Cu), and magnesium. (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), tantalum (Ta), titanium (Ti), tungsten (W), zinc (Zn), vanadium (V), brass (brass), bronze and one or more metals or alloys selected from the group consisting of bronze, white brass, stainless steel and germanium (Ge). When the substrate 10 is a metal, the substrate 10 may serve as a catalyst for forming the graphene thin film 20.

The method of forming the graphene thin film 20 on the substrate 10 is not limited. For example, the method may be exfolidation, sublimation (graphene formation on a SiC substrate), or chemical vapor deposition. Examples of chemical vapor deposition include high temperature chemical vapor deposition (RTCVD), inductively coupled plasma chemical vapor deposition (ICP-CVD), low pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition (APCVD), and metal organic chemical vapor deposition (MOCVD). ), And plasma chemical vapor deposition (PECVD), but are not limited thereto.

More specifically, when the reaction gas containing a carbon source (carbon monoxide, carbon dioxide, methane, ethane, benzene, etc.) is supplied to the substrate 10 and heat treated at a temperature of 300 ° C. to 2000 ° C. at normal pressure, The graphene thin film 20 may be formed by combining the existing carbon components to form a graphene layer having a plate-like structure. At this time, the pressure condition may be a case of low pressure or high pressure in some cases.

In the graphene thin film 20, a plurality of carbon atoms are covalently linked to each other to form a polycyclic aromatic molecule. The graphene thin film 20 may include a graphene layer of a single layer or a plurality of layers.

The support thin film 30 is for transporting the graphene thin film 20 and is attached to the graphene thin film 20. The attachment method is not limited, and a conventional solution process, deposition process, roll-to-roll process, polymerization process, or the like can be used.

The support thin film 30 may be made of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonate).

The PEDOT: PSS has high electrical conductivity, transparency, and excellent film forming properties, and thus is widely used in electronic devices such as light emitting devices (LEDs), optoelectronic devices, solar cells, and thin film transistors. Therefore, when PEDOT: PSS is used as the support thin film 30, the support thin film 30 to which the graphene thin film 20 is attached may be used in the electronic device without removing the support thin film 30. In addition, since PEDOT: PSS has an effect of alleviating the surface roughness of the graphene thin film 20, the PEDOT: PSS is more suitable for the application of the graphene thin film 20 to electronic devices.

In addition, when the PEDOT: PSS is used as the support thin film 30, the doping of the PEDOT: PSS may be increased by the influence of ion gas contained in the etching solution for etching the substrate 10. Therefore, since the conductivity of the support thin film 30 made of PEDOT: PSS may be increased, it may contribute to improving the characteristics of the electronic device to which the graphene thin film 20-support thin film laminate is applied. .

In the case where the support thin film 30 is made of PEDOT: PSS, the graphene thin film transfer method attaches the support thin film 30 to the graphene thin film 20, and then the substrate 10 -graphene thin film ( 20)-further comprising the step of immersing the laminate stacked in the order of the support thin film 30 in a polar solution.

At this time, the polar solution is ethylene glycol, dimethyl sulfoxide (DMSO), glycerol, N, N- dimethyl formamide (DMF), sorbitol, N-methyl pyrrolidone (NMP), nitromethane, acetonitrile and methanol It may be at least one solution selected from the group consisting of.

As described above, the reason why the laminate is immersed in the polar solution is to reinforce the holding force of the PEDOT: PSS. Specifically, after attaching the graphene thin film 20 to the support thin film 30, the substrate 10 is removed, and the supporting force of the PEDOT: PSS may be lowered by the etching solution used. Therefore, when the PEDOT: PSS is immersed in the polar solution as described above, while the PSS, which is a substance that enhances the solubility, is extracted from the PEDOT: PSS, the support force of the PEDOT: PSS may be reinforced. Of course, the step of immersing the laminate in a polar solution is optional, and in some cases may be omitted.

On the other hand, the support thin film 30 may be made of an organic polymer material in addition to the PEDOT: PSS.

In this case, the organic polymer material may be polyaniline, polypyrrole, polyacetylene, polyethylenedioxylthiophene, polyphenylenevinylene, polyfluorene, polyparaphenylene, polyalkylthiophene and polypyridine. At least one selected from the group consisting of may be a doped material. For example, the doping may be p-type.

In addition, the support thin film 30 may be made of a metal oxide material in addition to the PEDOT: PSS and the organic polymer material.

In this case, the metal oxide material is titanium (Ti), zinc (Zn), strontium (Sr), indium (In), barium (Ba), potassium (K), niobium (Nb), iron (Fe), tantalum ( Ta, tungsten (W), bismuth (Bi), nickel (Ni), copper (Cu), molybdenum (Mo), cerium (Ce), platinum (Pt), silver (Ag), rhodium (Rh) and ruthenium ( Ru) can be formed from one or more metal alkoxides selected from the group consisting of.

For example, a metal oxide intermediate solution may be formed by mixing a solvent and an additive with the metal alkoxide under the condition that oxygen and water are removed. Next, a metal oxide in a gel state may be formed by condensation by applying heat to the metal oxide intermediate solution, and a metal oxide solution may be formed using a dispersion. Next, the metal oxide solution may be attached to the graphene thin film 20 through the solution process as the support thin film 30. At this time, the solvent mixed with the metal alkoxide may be alcohols such as ethanol, methanol, isopropanol, and the additive may be alcohol amines such as ethanolamine, methanolamine, hydrogen peroxide or ammonium hydroxide.

As described above, the support thin film 30 may be made of PEDOT: PSS, an organic polymer material, or a metal oxide material. For convenience of explanation, hereinafter, the supporting thin film 30 will be described based on the case where PEDOT: PSS is manufactured.

2. Second Step

After attaching the support thin film 30 to the graphene thin film 20, the substrate 10 is removed (see FIG. 2C).

As a method of removing the substrate 10, various methods may be used according to the type of the substrate 10, for example, an etching process may be used. When an etching process is used, an etching solution including ammonium persulfate, HF, BOE, Fe (NO 3 ) 3, iron chloride (FeCl 3 ), or the like may be used, but is not limited thereto. In addition to the etching process, the substrate 10 may be removed by methods such as reactive ion etching, ion milling, and ashing.

The processes may be performed one or more times to remove the substrate 10. By performing the processes a plurality of times, the substrate 10 may be more completely removed.

On the other hand, after removing the substrate 10 may be further subjected to the process step of cleaning the laminate laminated in the order of the graphene thin film 20-support thin film 30. The cleaning process is to remove residues that may remain in the graphene thin film 20 after removal of the substrate 10, and may be performed using IPA (isopropyl alcohol), deionized water, or the like.

3. The third step

After the removal of the substrate 10, a device including a support thin film 30 to which the graphene thin film 20 is attached is manufactured as a functional layer (see FIG. 2D). The support thin film 30 to which the graphene thin film 20 is attached may function as a functional layer in the electronic device. In this case, the functional layer means, for example, a hole transport layer (HTL) in a solar cell, a light emitting device, or the like, a buffer layer or an intermediate electrode disposed between electrodes of a tandem organic device. On the other hand, in connection with the manufacturing of the device shown that the graphene thin film 20 is attached to the support thin film 30 is transferred to the transparent substrate 40 is shown.

In the graphene thin film transfer method according to an embodiment of the present invention, since the support thin film 30 is made of PEDOT: PSS, an organic polymer material or a metal oxide material, and thus has no insulator, the graphene thin film 20 is supported. It is possible for the thin film 30 to function as a functional layer in the electronic device.

In this case, the device may be a light emitting device (LED), an optoelectronic device, a solar cell, a thin film transistor, or an energy storage device, but is not limited thereto. That is, all of the electronic devices in which the laminate of the graphene thin film 20 and the support thin film 30 made of PEDOT: PSS, an organic polymer material or a metal oxide material may function as a functional layer may be included in the device.

As described above, in the embodiments of the present invention, the support thin film 30 to which the graphene thin film 20 is attached is included as a functional layer of the electronic device, thereby eliminating the need to separately remove the support thin film 30. It prevents deterioration of device characteristics and performance due to thin film removal process. In addition, since the electronic device can be manufactured without removing the supporting thin film, the manufacturing process of the electronic device can be simplified.

On the other hand, according to another aspect of the present invention, an electronic device manufactured by including a graphene thin film transfer method according to an embodiment of the present invention can be provided. The electronic device may be used in a light emitting device, an optoelectronic device, a solar cell, an organic thin film transistor, or an energy storage device.

Hereinafter, the present invention will be described in more detail with reference to test examples of the present invention. It should be understood, however, that the following test examples are illustrative only to illustrate the present invention, and do not limit the scope of the present invention.

Test Example

Comparative Example  And Example  Ready

For the test, Comparative Examples and Examples were prepared as shown in Table 1 below.

Support film Final laminate Remarks Comparative Example 1 PMMA Graphene thin film After transfer, rinsing Comparative Example 2 PMMA Graphene thin film Hot acetone treatment after transfer Comparative Example 3 PMMA Graphene Thin Film + PEDOT: PSS After transfer, rinsing and laminating PEDOT: PSS layer Comparative Example 4 PMMA Graphene Thin Film + PEDOT: PSS After transfer, hot acetone treatment and lamination of PEDOT: PSS layer Example PEDOT: PSS Graphene Thin Film + PEDOT: PSS

The biggest difference between the comparative examples and the examples lies in the material used as the support thin film. In Comparative Examples 1 to 4, PMMA was used as the supporting thin film, and in the case of Examples, PEDOT: PSS was used as the supporting thin film. On the other hand, in the case of Comparative Examples 1 and 2, the supporting thin film was removed after transfer, and in the case of Comparative Examples 3 and 4, the PEDOT: PSS layer was laminated after removing the supporting thin film.

More specifically, Comparative Examples 1 and 2 were laminated with a PMMA support thin film on a graphene thin film prepared on a substrate (Ni) by chemical vapor deposition, and in order to remove the support thin film after transporting in Comparative Example 1 as acetone The pin thin film-supported thin film laminate was rinsed. Meanwhile, in Comparative Example 2, the laminate was placed in a container containing acetone, and then the support thin film was removed by treating the laminate at a temperature of 70 ° C. for 10 minutes on a hot plate. After removing the support thin films in Comparative Examples 1 and 2, the mixture was washed once again using acetone, isopropyl alcohol (IPA), and DI water.

In Comparative Example 3, the PEDOT: PSS layer was laminated on the graphene thin film from which the support thin film was removed after the same process as in Comparative Example 1, and Comparative Example 4 supported the PEDOT: PSS layer after the same process as in Comparative Example 2. The thin film was laminated on the removed graphene thin film. The lamination was performed by coating using a spin coating method (2,000 to 5,000 rpm), followed by heat treatment at 150 ° C. for 10 minutes on a hot plate.

The embodiment was transferred by laminating a PEDOT: PSS support thin film on a graphene thin film prepared on a substrate (Ni) by chemical vapor deposition. The lamination was performed by coating using a spin coating method (2,000 to 5,000 rpm), followed by heat treatment at 150 ° C. for 10 minutes on a hot plate.

Sheet resistance ( Sheet resistivity ) Measure

Sheet resistance (surface resistance) was measured about the above-mentioned comparative examples and examples. Sheet resistance was measured by the van der Pauw method using the Hall measurement system equipment (hall resistance measurement equipment). Specifically, after preparing specimens having a square shape corresponding to Comparative Examples and Examples and attaching indium for probe contact to each vertex, four probes were contacted to each vertex to measure sheet resistance. The amount of current applied was 0.1 to 2 mA.

3 is a graph showing the sheet resistance measurement results of Comparative Examples and Examples.

Referring to FIG. 3, it was confirmed that the sheet resistance of Comparative Examples 3 and 4 and Examples in which PEDOT: PSS is included in the laminate is lower than in Comparative Examples 1 and 2 in which PEDOT: PSS is not included in the laminate. . In addition, Comparative Examples 3, 4 and Examples show a similar level of sheet resistance, and thus, when PEDOT: PSS is used as a supporting thin film, the same level of device characteristics may be secured without a separate removing of the supporting thin film. Confirmed.

Permeability measurement

Permeability was measured about the above-mentioned comparative examples and examples. The transmittance was measured using a UV / Vis / NIR spectrophotometer. Specifically, the measurement was performed at room temperature and in air using fused silica with little absorption in the UV and visible regions.

4 is a graph showing the results of measuring the transmittance of the Comparative Example and Example.

Referring to FIG. 4, the transmittances of Comparative Examples 3 and 4 in which PEDOT: PSS is included in the laminate and the transmittances of PEDOT: PSS are compared to Comparative Examples 1 and 2 in which PEDOT: PSS is not included in the laminate. Was measured to be lower (especially lower transmittance at wavelengths above 500 nm). In addition, Comparative Examples 3, 4 and Examples show similar levels of transmittance at a wavelength of 500 nm or more. Thus, when PEDOT: PSS is used as a support thin film, device characteristics at the same level are secured without a separate process of removing the support thin film. It can be confirmed that.

RMS roughness  And Current  Measure

5A to 5C are photographs of morphologies and currents of Comparative Examples 1 and 2 and Examples.

5A to 5C, the morphology and the current flowing in the graphene thin film were measured using atomic probe microscopes (Park Systems, XE-100) for conductivity measurement for Comparative Examples 1 and 2 and Examples. The measurement conditions were obtained by applying atomic probe microscopy images by applying a 0.5V voltage to each specimen and grounding the probe and contacting at a speed of 0.2 Hz to 0.3 nN and a speed of 1 Hz.

In the photograph of FIGS. 5A to 5C, the left side shows a morphology for checking surface roughness, and the right side shows a current flow distribution (the more bright parts, the smoother the current flow). 5A (Comparative Example 1) and FIG. 5B (Comparative Example 2), it can be seen that many residues appear on the surface of the graphene thin film, whereas in FIG. 5C (Example), there is almost no such residue. You can check it. In addition, in FIG. 5A (Comparative Example 1), almost no current flows due to the PMMA residue (non-conductive residue). In FIG. 5B (Comparative Example 2), the current flows only partially, whereas in FIG. 5C (Example) As no residue remains, it can be seen that the current flows smoothly. In addition, in FIG. 6, it is clear that the surface roughness and the current measurement results described above with respect to Comparative Examples 1 and 2 and Examples are illustrated in a graph.

Organic solar cell manufacturing

Organic solar cells to which Comparative Examples 1,2 and Examples were applied were prepared, respectively. Organic solar cells are manufactured in two types with different donor materials. In the case of the first organic solar cell, PTB7-F40 was used as the donor material, and in the case of the second organic solar cell, PCDTBT was used as the donor material. Since the organic solar cells are manufactured in the same or similar manner, the following description will briefly describe a manufacturing process of the first organic solar cell.

In order to manufacture a 1st organic solar cell, the laminated body corresponding to the comparative example 1,2 and the Example was provided as a 1st electrode on the glass substrate, respectively. Next, PTB7-F40 as a donor material and PC 71 BM as an acceptor material were blended in chlorobenzene, and then 3 vol% of diiodooctane was added to PTB7-F40: PC 71 BM (DIO). After the solution was prepared, the solution was coated to a thickness of 120 nm using spin coating to form a first organic photoactive layer.

Next, a titanium precursor sol is prepared in a nitrogen atmosphere using titanium (IV) isopropanol, 2-methoxyethanol and ethanolamine, and the spin-coating method is used to prepare the first organic solvent. Coating on the photoactive layer to form a first charge transport layer. The coated titanium precursor sol formed a titanium oxide film (n-type semiconductor material layer) through a sol-gel reaction. Next, Al, which is a second electrode, was deposited on the first charge transport layer.

7 is a graph showing I-V curves and PCE (energy conversion efficiency) measurement results of the first organic solar cell, and FIG. 8 is a graph showing I-V curves and PCE (energy conversion efficiency) measurement results of the second organic solar cell.

Referring to FIGS. 7 and 8, it can be seen that the energy conversion efficiency of Examples 1 and 2 is higher than that of Comparative Examples 1 and 2 in both the first and second organic solar cells. Therefore, when using PEDOT: PSS as a support thin film as in the embodiment, it was confirmed that a device having a high light conversion efficiency can be implemented.

PEDOT : PSS Thin film  Doping Effect During Transfer

In order to examine the doping effect during the transfer process of the PEDOT: PSS support thin film, the light absorption rate after the PEDOT: PSS coating on the glass and the thin film of iron chloride (FeCl 3 ) was allowed to stand for a certain time was compared.

In this regard, Figure 9 is a graph comparing the light absorption rate before and after the iron chloride treatment.

Referring to FIG. 9, it can be seen that the glass-PEDOT: PSS thin film treated with iron chloride (solution) increases light absorption in the wavelength range of 900 to 1500 nm than otherwise. Increasing the light absorption can be seen as an increase in the degree of doping, it can be seen that the doping of the PEDOT: PSS layer due to the chlorine vapor in the iron chloride treatment process. The increased doping results in a resistance reduction effect, which shows that the conductivity can be improved during the removal of the substrate for transport in the graphene thin film-PEDOT: PSS support thin film laminate.

Meanwhile, the above-described second organic solar cell was manufactured by the same or similar method. At this time, PEDOT: PSS was applied onto an indium tin oxide (ITO) electrode as a first electrode. In addition, after dividing the first electrode according to the presence or absence of iron chloride treatment, each of the second organic solar cells was manufactured to measure current density.

In this regard, Figure 10 is a graph of the I-V curve with or without iron chloride treatment.

Referring to FIG. 10, the device using the ITO-PEDOT: PSS thin film treated with iron chloride (solution) has a larger current and voltage than the other case, and thus, the conversion efficiency is increased. Therefore, the doping effect of the device performance is improved in the process of transporting the graphene using the PEDOT: PSS support thin film.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention as set forth in the appended claims. The present invention can be variously modified and changed by those skilled in the art, and it is also within the scope of the present invention.

1, 10: substrate
2, 20: graphene thin film
3, 30: support film
4, 40: transparent substrate

Claims (9)

A first step of attaching a support thin film to the graphene thin film formed on the substrate;
A second step of removing the substrate; And
Graphene thin film transfer method comprising the third step of manufacturing a device comprising a support thin film to which the graphene thin film is attached as a functional layer. The method according to claim 1,
The graphene thin film is a graphene thin film transfer method formed by chemical vapor deposition. The method according to claim 1,
The support thin film is a graphene thin film transfer method made of PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonate). The method according to claim 3,
Between the first step and the second step,
The graphene thin film transport method further comprising the step of immersing the substrate, the graphene thin film and the support thin film laminated in a polar solution. The method of claim 4,
The polar solution consists of ethylene glycol, dimethyl sulfoxide (DMSO), glycerol, N, N-dimethyl formamide (DMF), sorbitol, N-methyl pyrrolidone (NMP), nitromethane, acetonitrile and methanol Graphene thin film transfer method is one or more solutions selected from. The method according to claim 1,
The support thin film is made of an organic polymer material,
The organic polymer material may be selected from the group consisting of polyaniline, polypyrrole, polyacetylene, polyethylenedioxylthiophene, polyphenylenevinylene, polyfluorene, polyparaphenylene, polyalkylthiophene and polypyridine. Graphene thin film transfer method of at least one selected doped material. The method according to claim 1,
The support thin film is made of a metal oxide material,
The metal oxide material is titanium (Ti), zinc (Zn), strontium (Sr), indium (In), barium (Ba), potassium (K), niobium (Nb), iron (Fe), tantalum (Ta), With tungsten (W), bismuth (Bi), nickel (Ni), copper (Cu), molybdenum (Mo), cerium (Ce), platinum (Pt), silver (Ag), rhodium (Rh) and ruthenium (Ru) Graphene thin film transfer method formed from at least one metal alkoxide selected from the group consisting of. The method according to claim 1,
The device of claim 3, wherein the device is a light emitting device, a photoelectric device, a thin film transistor or an energy storage device. An electronic device manufactured by including the graphene thin film transfer method according to any one of claims 1 to 8.
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