KR20130014323A - Hybrid organic-inorganic thin film and producing method of the same - Google Patents

Abstract

PURPOSE: An organic-inorganic hybrid thin film and a manufacturing method thereof are provided to form an expanded structure with a strong covalent bond, thereby securing not only an excellent thermo-stability and a mechanical stability but also a high carrier-mobility. CONSTITUTION: A manufacturing method of an organic-inorganic hybrid thin film includes a step of interlaying an inorganic cross-linking layer with a conjugate organic polymer through MLD(Molecular Layer Deposition). The manufacturing method includes a step of binding the inorganic cross-linking layer on a substrate inside an MLD chamber, and a step of polymerizing HDD(Hexadiyne Diol) coupled to the inorganic cross-linking layer on the substrate with UV(ultraviolet) treatment. A process cycle is implemented at least one time. The organic polymer includes polyacethylene or vinyl ether-aleimide. The inorganic cross-linking layer includes a metallic oxide selected from a group of Zn, Al, Ti, Zr, Sn, Mn, Fe, Ni, Mo, and combination thereof. The organic-inorganic hybrid thin film is two dimensional.

Description

HYBRID ORGANIC-INORGANIC THIN FILM AND PRODUCING METHOD OF THE SAME

The present application is a method for producing an organic-inorganic hybrid thin film comprising interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD), an organic-inorganic hybrid thin film produced by the manufacturing method and the An organic electronic device and a thin film transistor including an organic-inorganic hybrid thin film .

Many materials used in organic electronic devices are conjugated organic polymers with crossed double and single bond backbones through which electrons can flow. Due to their structural flexibility and variable electronic properties, conductive polymers are flexible and inexpensive and can be applied to many applications such as flexible displays, radio frequency identification devices (RFIDs), smart cards, nonvolatile memories and sensors. Can be. These polymers have one-dimensional properties, and the thin film of conjugated polymer has a disordered structure in which each polymer strand is twisted and bent. In most applications, attempts have been made to uniformly align polymer chains to control the efficiency with which light and electrons can be transported by polymer molecules. Republic of Korea Patent No. 10-0957528 describes a method for producing a cross-linked organic-inorganic hybrid composite material using a small amount of inorganic oxide particles and a silicon-based cross-linked polymer precursor.

In order to solve the above problems, the inventors of the present application have found that by incorporating a stable inorganic crosslinking layer into a conjugated organic polymer, the inventors have found that they can better control the arrangement, stability, and electronic properties of the organic polymer chains.

Accordingly, the present application includes a method for preparing an organic-inorganic hybrid thin film and an organic-inorganic hybrid prepared by the method, which include interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD). To provide a thin film. In addition, the present application is to provide an organic electronic device and a thin film transistor including the organic-inorganic hybrid thin film.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

A first aspect of the present disclosure provides a method for preparing an organic-inorganic hybrid thin film, which comprises interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD).

A second aspect of the present disclosure provides an organic-inorganic hybrid thin film prepared by the first aspect of the present disclosure.

A third aspect of the present application provides an organic electronic device comprising an organic-inorganic hybrid thin film according to the second aspect of the present application.

A fourth aspect of the present disclosure, the substrate; A semiconductor channel comprising an organic-inorganic hybrid thin film according to the second aspect of the present application formed on said substrate; And a source / drain electrode formed on the semiconductor channel.

The organic-inorganic hybrid thin film prepared by the method for preparing an organic-inorganic hybrid thin film, which comprises intercalating an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD) of the present application, may be formed of an inorganic crosslinked layer. The conjugated organic polymer layer may be combined to form a two-dimensional organic-inorganic hybrid thin film. The inorganic layer of the organic-inorganic hybrid thin film of the present disclosure constitutes an extended structure bonded by strong covalent bonds, giving high carrier mobility as well as excellent thermal stability and mechanical stability. In addition, molecular layer deposition (MLD), as used herein, enables precise control of film thickness, large scale uniformity, good conformality, good reproducibility, and sharp interface at low temperatures. The organic-inorganic hybrid thin films of the present disclosure exhibit excellent thermal and mechanical stability, and high field effect mobility (> 1.3 cm ² V ⁻¹ s). The MLD method is an ideal technique for the production of various organic-inorganic hybrid thin films having an inorganic crosslinked layer, and can also be applied to the production of organic polymer-inorganic hybrid superlattices.

1 is a schematic diagram showing a process of interlayer bonding an inorganic crosslinked layer and an organic polymer by a molecular layer deposition method according to an embodiment of the present application.
Figure 2 is a schematic diagram showing a process of interlayer bonding the inorganic cross-linking layer and the organic polymer by a molecular layer deposition method according to an embodiment of the present application.
3 is a graph showing the thickness of a ZnOPDA film as a function of DEZ input time (a) and a function of HDD input time (b) in one embodiment of the present application.
4 shows a graph (b) and an AFM image (c) showing the relationship between the thickness of the ZnOPDA film and the number of MLD cycles (a) in the TEM image (a) of the ZnOPDA film.
Figure 5 shows the Raman spectrum (a) and XP spectrum (b) of the ZnOPDA film according to an embodiment of the present application.
FIG. 6 shows a photoluminescence spectrum of a PDA film without ZnOPDA and an inorganic crosslinking layer in one embodiment of the present application.
7 is a cross-sectional view of a TFT having a ZnOPDA active layer on a high-doped Si substrate, in one embodiment of the present disclosure.
8 is a graph illustrating a drain current-drain voltage ( I _D - V _D ) output curve of a TFT according to an embodiment of the present disclosure.
FIG. 9 is a graph illustrating drain current-gate voltage I _D - V _G transition curves and gate leakage levels of a TFT according to an exemplary embodiment of the present disclosure.
FIG. 10 shows infrared spectral spectra of TiOPDA films and precursors, in accordance with an embodiment of the present disclosure. FIG.
FIG. 11 shows UV-VIS spectroscopy spectra of TiOPDA films and precursors, in accordance with an example herein.
12 shows an XPS graph of a TiOPDA film, according to an embodiment of the present disclosure.

Hereinafter, embodiments and examples of the present application will be described in detail so that those skilled in the art can easily practice.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise. As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided to aid the understanding herein. In order to prevent the unfair use of unscrupulous infringers. In addition, throughout this specification, "step to" or "step of" does not mean "step for."

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

A first aspect of the present disclosure provides a method for preparing an organic-inorganic hybrid thin film, which comprises interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD).

According to one embodiment of the present application, the method of preparing the organic-inorganic hybrid thin film may include: bonding an inorganic crosslinking layer on a substrate in an MLD chamber; And bonding hexadiyne diol (HDD) to the inorganic crosslinked layer bonded on the substrate. It may include, but is not limited to, performing one or more process cycles including UV treating and polymerizing.

The MLD is a gas-phase layered growth method, similar to atomic layer deposition (ALD), in which organic monolayers are formed in each order by sequential saturated surface reactions. In one embodiment of the present application, the inorganic crosslinked layer and the conjugated organic polymer layer may be combined to form 2D polydiacetylene using the MLD. The inorganic layer constitutes an extended structure bonded by strong covalent bonds, giving high carrier mobility as well as excellent thermal and mechanical stability. The advantages of MLD technology are that it enables precise control of film thickness at low temperatures, large scale uniformity, good conformality, good reproducibility, multilayer processing capability, sharp interface and good film quality at low temperatures. For example, the 2D polydiacetylene thin film has a ligand-exchange reaction between the inorganic crosslinked layer and hexadiyne diol (HDD) by UV polymerization, so that OH groups at both ends of the diol react sequentially with the inorganic crosslinked layer. By generating cross-linked alkanes, it can be configured to have monolayer precision. Inorganic oxide cross-linked polydiacetylene thin films exhibit increased carrier mobility or other properties due to their 2D structure.

1 and 2, a method of manufacturing an organic-inorganic hybrid thin film according to one embodiment of the present application will be described.

FIG. 1 schematically illustrates a process of preparing a zinc oxide cross-linked polydiacetylene (ZnOPDA) thin film using diethylzincl DEZ as an inorganic crosslinking layer. The substrate is exposed to form an ethyl zinc monolayer. DEZ molecules are covalently adsorbed on the surface of the hydroxyl-rich substrate via ligand-exchange reactions to form C ₂ H ₅ ZnO species. Then, the ethyl group of the chemisorbed ethyl zinc molecule on the substrate is substituted with the OH group of the HDD having living ethane to form a diacetylene layer, and the OH group of the diacetylene layer is used for the exchange reaction of the next DEZ molecule. Provide the active site. The diacetylene molecules are then polymerized by UV irradiation to form a polydiacetylene layer. A zinc oxide cross-linked polyacetylene (ZnOPDA) thin film is grown under vacuum by sequentially repeating adsorption and UV polymerization of DEZ and HDD. The expected monolayer thickness of ZnOPDA's ideal model structure is about 6 GPa, but is not limited thereto.

FIG. 2 schematically shows a process for preparing a titanium oxide cross-linked polydiacetylene (TiOPDA) thin film using TiCl ₄ as an inorganic crosslinking layer, exposing a substrate to TiCl ₄ molecules in an MLD chamber. To form a titanium dichloride monolayer. TiCl ₄ molecules are adsorbed onto the surface of the hydroxy group rich substrate via a ligand-exchange reaction. Then, the chlorine group of the titanium dichloride molecule chemisorbed on the substrate is substituted with the OH group of the HDD having living ethane to form a diacetylene layer, and the OH group of the diacetylene layer exchanges the following TiCl ₄ molecules It provides an active site for. The diacetylene molecules are then polymerized by UV irradiation to form a polydiacetylene layer. Titanium oxide cross-linked polyacetylene (TiOPDA) thin film is grown under vacuum by sequentially repeating adsorption and UV polymerization of TiCl ₄ and HDD.

According to one embodiment of the present application, the organic polymer may be used without limitation as long as it is an initiator-free photopolymerizable polymer that does not have an initiator for initiating polymerization, for example, polydiacetylene or vinyl ether. It may be, but is not limited to, vinyl ether-aleimide.

According to one embodiment of the present application, the inorganic crosslinked layer may include an oxide of a metal selected from the group consisting of Zn, Al, Ti, Zr, Sn, Mn, Fe, Ni, Mo, and combinations thereof, It is not limited to this. The inorganic crosslinked layer forms a hybrid organic-inorganic structural material, allowing better control of the arrangement, stability and electronic properties of the organic polymer chains. The stable and excellent electrical properties of the inorganic components plus the structural flexibility and variable optoelectronic properties of the organic components make the organic-inorganic hybrid conductive polymers an ideal material for use in organic electronic devices.

According to one embodiment of the present application, the organic-inorganic hybrid thin film may be two-dimensional, but is not limited thereto.

According to the exemplary embodiment of the present invention, when the hexadiin diol (HDD) is bound to the inorganic crosslinked layer bonded on the substrate, it may include self-terminating reaction, but is not limited thereto. It is not. In the MLD, in order to produce a uniform, conformal and high-quality polydiacetylene thin film, it is preferable that the surface reaction of the HDD is self-terminating and complementary.

According to one embodiment of the present disclosure, the inorganic crosslinking layer may be bonded on the substrate and then purged, but the present invention is not limited thereto.

According to the exemplary embodiment of the present invention, the method may further include purging the hexadiin diol (HDD) to the inorganic crosslinked layer bonded on the substrate, but is not limited thereto.

According to the exemplary embodiment of the present application, the purge gas may be purged using argon (Ar), nitrogen (N ₂ ), helium (He), and the like, but is not limited thereto.

The second aspect of the present application provides an organic-inorganic hybrid thin film prepared by the method for producing an organic-inorganic hybrid thin film of the first aspect of the present application.

According to one embodiment of the present invention, the organic-inorganic hybrid thin film may be two-dimensional, but is not limited thereto.

A third aspect of the present application provides an organic electronic device comprising an organic-inorganic hybrid thin film according to the second aspect of the present application.

A fourth aspect of the present disclosure, the substrate; A semiconductor channel comprising an organic-inorganic hybrid thin film according to the second aspect of the present application formed on said substrate; And a source / drain electrode formed on the semiconductor channel.

According to the exemplary embodiment of the present disclosure, the thin film transistor may have a field effect mobility of about 1.2 cm ² V ⁻¹ s to about 1.7 cm ² V ⁻¹ s, but is not limited thereto.

Hereinafter, the present application will be described in detail using examples. However, the present application is not limited thereto.

[ Example ]

matter

Unless otherwise noted, all commercially available materials are listed in Aldrich Chemical Co. It was purchased from and used without further purification. 2,4-hexadiyne-1,6-diol (2,4-Hexadiyne-1,6-diol; HDD) was purchased from Tokyo Chemical Industry. Deionized water was purified using the Millipore Milli Q Plus system, distilled over KMnO ₄ and passed through the Millipore Simplicity system.

Example  One

Preparation of Substrate

Si substrates were prepared by cutting p-type (100) wafers (LG Siltron) having a resistivity in the range of 1-5 Ωm. Si substrates were treated by a chemical cleaning procedure proposed by Ishizaka and Shiraki (A. Ishizaka, Y. Shiraki, J. Electrochem. Soc. 1986, 133, 666-671), which process was performed by dressing, HNO ₃ Heating in HNO ₃ / H ₂ O (alkali treatment), heating in HCl (acid treatment), washing with deionized water and blowing-drying with nitrogen to remove contaminants and grow a thin protective oxide layer on the surface It involves making.

Molecular layer  deposition

The oxidized Si (100) substrate was introduced into Cyclic 4000 MLD system (Genitech, Taejon, Korea). Zinc oxide cross-linked polydiacetylene (ZnOPDA) thin films were deposited on the substrate using DEZ and HDD as precursors. Argon was fed as both the carrier gas and the purge gas. DEZ and HDD were evaporated at 20 ° C. and 80 ° C., respectively. The cycle consisted of exposing to DEZ for 2 seconds, purging with Ar for 10 seconds, exposing to HDD for 10 seconds, and purging with Ar for 50 seconds. The total flow rate of Ar was 50 sccm. The deposited HDD layer was exposed to UV light (λ = 254 nm, 100 W) for 30 seconds. ZnOPDA films were grown at a temperature of about 100 ° C. to about 150 ° C. under a pressure of 300 mTorr.

Example  2

Preparation of Substrate

Si substrates were prepared by cutting p-type (100) wafers (LG Siltron) having a resistivity in the range of 1-5 Ωm. Si substrates were treated by a chemical cleaning procedure proposed by Ishizaka and Shiraki (A. Ishizaka, Y. Shiraki, J. Electrochem. Soc. 1986, 133, 666-671), which process was performed by dressing, HNO ₃ Heating in HNO ₃ / H ₂ O (alkali treatment), heating in HCl (acid treatment), washing with deionized water and blowing-drying with nitrogen to remove contaminants and grow a thin protective oxide layer on the surface It involves making.

Molecular layer  deposition

The oxidized Si (100) substrate was introduced into Cyclic 4000 MLD system (Genitech, Taejon, Korea). Zinc oxide cross-linked polydiacetylene (TiOPDA) thin films were deposited on the substrate using TiCl ₄ and HDD as precursors. Argon was fed as both the carrier gas and the purge gas. TiCl ₄ and HDD were evaporated at 20 ° C. and 80 ° C., respectively. The cycle consisted of exposing to TiCl ₄ for 2 seconds, purging with Ar for 10 seconds, exposing to HDD for 10 seconds, and purging with Ar for 50 seconds. The total flow rate of Ar was 50 sccm. The deposited HDD layer was exposed to UV light (λ = 254 nm, 100 W) for 30 seconds. The TiOPDA film was grown at a temperature of about 100 ° C. to about 150 ° C. under a pressure of 300 mTorr.

Experimental Example  One

Example  1 of ZnOPDA  Investigate the properties of the film

Raman spectra of ZnOPDA films prepared as in Example 1 were obtained using a Raman spectroscopy system (Renishaw Model 2000) equipped with a built-in microscope (Olympus BH2-UMA). A 514.5 nm line from a 20 mW air-cooled Ar ⁺ laser (Melles-Griot Model 351mA520) was used as the excitation source. Raman scattering was detected with 180 ° geometry using a Peltier-cooled (-70 ° C.) charge-coupled device (CCD) camera. 520 cm ^- the Raman bands of the silicon wafer in the ^first was used to adjust the spectrometer. All XP spectra were recorded on a ThermoVG SIGMA PROBE spectrometer using an Al _Ka source operating at 15 kV and 70 W. The binding energy scale was adjusted to 285 eV at the main C 1s peak. Each sample was analyzed at 90 ° against an electronic analyzer. The thickness of the polymer film was measured by an ellipsometer (AutoEL-II, Rudolph Research) and transmission electron microscope (TEM; JEM2100F, JEOL). The current-voltage curve of the TFT was measured with a semiconductor parameter analyzer (HP4155C, Agilent Technologies). Optical properties were measured by photoluminescence (PL) spectroscopy using a He-Cd laser (325 nm) with a spectrometer (Darsa, PSI Co. Ltd.).

result

In an accurate MLD process, surface reactions must be self-terminating and complementary to produce uniform, conformal and high-quality polydiacetylene thin films. In order to confirm that the surface response to the HDD is actually self-terminating, the dosing time was varied from 1 second to 20 seconds. The growth rate of the ZnO-PDA film was measured using an ellipsometer at a growth temperature in the range of about 100 ° C to 150 ° C. The film thickness obtained per cycle for the HDD was saturated when the dosing time exceeded 10 seconds (FIG. 3B). This result indicates that the HDD had a self-termination reaction with DEZ adsorbed on the Si substrate. 3A shows that the growth rate rapidly saturates as a function of DEZ dosing time when the pulse time exceeds 0.5 seconds. These results indicate that DEZ had a rapid self-termination reaction with the HDD adsorbed on the substrate. All self-terminated growth experiments were performed at least 100 cycles. Saturation data indicate that DEZ and HDD are fully reactive with active sites on the surface and that the reaction does not persist after saturation, even in the presence of excess precursors.

The thickness of the ZnOPDA thin film as a function of the number of MLD cycles was measured using transmission electron microscopy (TEM) (FIG. 4A). TiO ₂ is added for color display.

These TEM images confirmed the prediction of monolayer thickness and MLD growth rate of ZnOPDA film. Figure 4b shows that the polydiacetylenes thickness increases almost linearly with increasing number of cycles, indicating that the surface action in the MLD process is complementary and complete. The growth rate measured is about 5.2 ms per cycle, which is consistent with the ellipsometer results. TEM images also showed that the ZnOPDA film was amorphous and did not have ZnO nanocrystals. The AFM image of the ZnOPDA film showed a very smooth and uniform surface and the root mean square (RMS) roughness of the surface was as low as 2.5 kHz (FIG. 4C). This is compared to the surface roughness of the initially washed Si substrate about 2.1 kPa. Regardless of the number of cycles, the surface of the ZnOPDA film was as smooth as the initially washed Si substrate, indicating that MLD growth was grown in a 2D fashion through layered growth and evenly doped across the substrate. These results suggest that the MLD of 2D polydiacetylene is self-limiting and progresses by laminar growth, and that the MLD conditions are sufficient to fully react at temperatures of about 100 ° C to about 150 ° C.

The temperature stability of the ZnOPDA film was confirmed using TEM. ZnOPDA films were stable in air up to a temperature of about 400 ° C. This result confirms that the polydiacetylene is covalently bonded by the zinc oxide crosslinking layer with the stability of the 2D polydiacetylene surviving in the TEM manufacturing process.

Surface-enhanced Raman scattering (SERS) spectroscopy was performed to confirm the photopolymerization of the diacetylene thin film. 100 nm thick Ag film was deposited on a Si (100) substrate using a vacuum evaporator. A 2 nm thick 2D polydiacetylene film was grown on Ag film. Ag nanoparticles of 60 nm diameter were dropped on the polydiacetylene surface under ambient conditions. 5A shows representative SERS spectra for ZnOPDA films located between Ag nanoparticles and Ag films. Three Raman bands were evident at ν ₁ = 2127 cm- ¹ , ν ₂ = 1525 cm ^-1 , and ν ₃ = 1060 cm ^-1 , which is quite consistent with the Raman data already observed for polydiethylene monolayers. It was. The narrow band at 2917 cm ⁻¹ is due to CH vibration. The remarkable and broad bands around 1590 and 1360 cm ⁻¹ are similar to those observed by irradiation with an excitation laser, which is interpreted as the result of conversion from polydiacetylene to a carbon material comprising graphite, amorphous carbon. The SERS results indicate that the diacetylene molecules of the film were polymerized by UV irradiation, which is consistent with the known photopolymerization of diacetylene.

X-ray photoelectron (XP) spectroscopic studies were conducted to determine the composition of ZnOPDA thin films grown by the MLD process. Figure 5b shows the irradiation spectrum of a 100 nm thick polydiacetylene thin film grown on a Si substrate. XP spectra show optoelectronic and Auger electron peaks for only zinc, oxygen and carbon. The peak area ratio for this element is 1: 3.2: 5.8 (Zn: O: C), which is corrected by the element sensitivity factor. For comparison, the expected ratio of the model structure of 2D polydiacetylene (FIG. 1) was 1: 2: 6. As such, the ratio of Zn: O: C of the present application 1: 3.2: 5.8 was found to be very similar to the ideal Zn: O: C ratio. The higher oxygen atom percentage can be explained by the adsorption of H ₂ O onto the ZnOPDA film. Water is mostly present on the surface of the film because the O 1s peak is significantly reduced compared to other peaks after Ar ion sputtering.

The photoluminescence (PL) spectrum of the ZnOPDA thin film is shown in FIG. 6. For PL spectra, a 100 nm thick polydiacetylene film deposited on a Si substrate was irradiated with a He-Cd laser (λ = 325 nm) as the excitation source. In Figure 6 it can be seen a broad peak around 500 nm. The PL spectrum shows the possibility of using ZnOPDA films in optical devices that include electroluminescence. For comparison, a polydiacetylene (PDA) thin film without the use of an inorganic crosslinked layer is also a methanol solution of 2,4-hexadiyne-1,6-diol (2,4-hexadiyne-1,6-diol; HDD) It was prepared by. 6 mM HDD dissolved in methanol was spin coated on the Si substrate for 1 minute at 1000 rpm, and then the substrate was exposed to UV light for 10 minutes to form a 100 nm thick PDA film. The spectrum of the resulting film is very similar to ZnOPDA but slightly shifted towards long wavelengths (FIG. 6). As such, it was confirmed that the ZnOPDA film produced by the organic-inorganic hybrid thin film manufacturing method of the present disclosure showed a photoluminescence result similar to that of polydiacetylene.

In order to investigate the electrical properties of the 2D polydiacetylene thin film, a thin film transistor (TFT) was fabricated by applying a ZnOPDA film as an active layer. The TFT has a ZnO-PDA semiconductor channel grown on a 100 nm thick SiO 2 / n ⁺ -Si substrate at 100 ° C. as seen in the device shown in FIG. 7. Patterned Al source / drain electrodes were vacuum-deposited on ZnOPDA film using a shadow mask. As can be seen in FIG. 8, a typical output (drain current vs. drain voltage: I _D - V _D ) curve was obtained from the ZnOPDA TFT. The data indicate that ZnOPDA acts as an n-type semiconductor. Maximum I _D level was about 40 μA under 100 V gate bias. According to the transition characteristics ( I _D - V _G ) which can be seen in FIG. 9, the high field effect electron mobility of 1.3 cm ² V ^-1 s or more has an on / off ratio of 10 ⁶ or more and a threshold voltage of 45 V. In saturation at V _D = 100 V. The gate leakage current ( I _G ) was less than 10 ^-10 A. The electron mobility is the highest among polydiacetylene-based TFTs. Such a ZnOPDA TFT can increase the operating speed of the flexible electronic device. A TFT with a 30 nm thick PDA was prepared without the crosslinking layer, which exhibited significantly lower field-effect mobility (<10 ⁻⁸ cm ² V ⁻¹ s) compared to ZnOPDA films.

As a result, two-dimensional polydiacetylene having an inorganic crosslinked layer was developed using MLD. The MLD process enables precise control of film thickness at low temperatures, large scale uniformity, good conformality, good reproducibility and sharp interface. The prepared ZnOPDA films exhibited excellent thermal and mechanical stability, and high field effect mobility (> 1.3 cm ² V ⁻¹ s). The MLD method is an ideal technique for the production of various 2D organic polymer thin films having an inorganic crosslinked layer, and can also be applied to the production of organic polymer-inorganic hybrid superlattices.

Experimental Example  2

Example  2 of TiOPDA  Investigate the properties of the film

An FTIR spectrometer (FTLA 2000) obtained the IR spectrum. The spectra were 64 scans at ¹ cm ⁻¹ intervals. Using a mortar and pestle, KBr powder (Sigma Aldrich) was ground finely, and KBr pellets were prepared using a compactor. TiOPDA was prepared in the same manner as in Example 2 after Al ₂ O ₃ was deposited using ALD technology to make hydroxyl sites on the prepared pellet surface. UV-VIS spectra of TiOPDA films prepared as in Example 2 above were obtained on a quartz plate (JMC glass) using a UV-VIS spectrometer (Agilent 8453 UV-Vis). All XP spectra were recorded on a VG Scientific ESCALAB MK II spectrometer using MgKa sources operating at 15 kV and 70 W. The binding energy scale was adjusted to 284.5 eV at the main C 1s peak. Each sample was analyzed at 90 ° against an electronic analyzer.

result

FTIR spectroscopy was used to identify the functional groups of the TiOPDA thin film. 10 shows the spectrum of the prepared TiOPDA thin film. PDA IR spectra were also analyzed for comparison. The peaks at 1000 cm ⁻¹ and 1350 cm ⁻¹ represent the peaks of the CO and CH ₂ bonds, respectively. A prominent peak at 1600 cm ⁻¹ is a peak for C = C stretching, indicating that diacetylene was polymerized by UV irradiation.

UV-VIS spectroscopy was used to evaluate the optical properties of TiOPDA. 11 is a 50 nm thick TiOPDA UV-VIS spectrum grown on a quartz plate. In comparison with diacetylene, TiOPDA showed absorption peaks in the wavelength region of 300 nm to 400 nm.

X-ray photoelectron (XP) spectroscopic studies were conducted to determine the composition of TiOPDA thin films grown by the MLD process. 12 shows the irradiation spectrum of a 100 nm thick TiOPDA thin film grown on a Si substrate. XP spectra showed optoelectronic and Auger electron peaks for only titanium, oxygen and carbon. The peak area ratio for this element is 1: 5.6: 11.7 (Ti: O: C), which is corrected by the element sensitivity factor. For comparison, the expected ratio of the model structure of 2D polydiacetylene (FIG. 2) was 1: 4: 12. Thus, it was confirmed that the ratio of Ti: O: C of 1: 5.6: 11.7 is very similar to the ideal Ti: O: C ratio. The C1s peak of 284.5 eV represents conjugated carbon, and the peaks of 286 and 288.6 eV are the peaks of carbon bonded to oxygen.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .

Claims (15)

A method for producing an organic-inorganic hybrid thin film, comprising interlayer bonding an inorganic crosslinked layer and an organic polymer through molecular layer deposition (MLD). The method of claim 1,
Bonding an inorganic crosslinked layer onto the substrate in the chamber for molecular layer deposition; And
Bonding hexadiyne diol (HDD) to the inorganic crosslinked layer bonded on the base, and then polymerizing the same by UV treatment.
Method for producing an organic-inorganic hybrid thin film comprising performing one or more process cycles comprising. The method of claim 1,
The organic polymer comprises polydiacetylene or vinyl ether-aleimide (vinyl ether-aleimide), a method for producing an organic-inorganic hybrid thin film. The method of claim 1,
The inorganic crosslinked layer includes an oxide of a metal selected from the group consisting of Zn, Al, Ti, Zr, Sn, Mn, Fe, Ni, Mo, and combinations thereof. . The method of claim 1,
The organic-inorganic hybrid thin film is a two-dimensional, organic-inorganic hybrid thin film manufacturing method. The method of claim 2,
When the hexadiin diol (HDD) is bonded to the inorganic cross-linked layer bonded on the substrate, self-terminating the reaction comprising, a method for producing an organic-inorganic hybrid thin film. The method of claim 2,
Bonding the inorganic crosslinking layer on the substrate and then further comprising purging, the organic-inorganic hybrid thin film manufacturing method. The method of claim 2,
Bonding the hexadiyne diol (HDD) to the inorganic crosslinked layer bonded to the substrate and further comprising purging, organic-inorganic hybrid thin film manufacturing method. The method of claim 7, wherein
The purging is to purge with a purge gas containing argon (Ar), nitrogen (N ₂ ) or helium (He), the organic-inorganic hybrid thin film manufacturing method. The method of claim 8,
The purging is to purge with a purge gas containing argon (Ar), nitrogen (N ₂ ) or helium (He), the organic-inorganic hybrid thin film manufacturing method. An organic-inorganic hybrid thin film prepared by the method for producing an organic-inorganic hybrid thin film according to any one of claims 1 to 10. The method of claim 11,
The organic-inorganic hybrid thin film is two-dimensional, organic-inorganic hybrid thin film. An organic electronic device comprising the organic-inorganic hybrid thin film of claim 11. temperament;
A semiconductor channel comprising the organic-inorganic hybrid thin film according to claim 11 formed on the substrate; And
Source / drain electrodes formed on the semiconductor channel
It includes, a thin film transistor. 15. The method of claim 14,
Wherein the thin film transistor has a field effect mobility of 1.2 cm ² V ⁻¹ s or more.

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