Electrically conductive film and electronic device comprising the same

Cross-reference to related applications

The request submission 27 May 2014 in the Korean Intellectual property office of the Korean Patent application No. 10-2014-0064011 of preferences and interests, all of its contents will be introduced as a reference herein.

Technical Field

Discloses conductive film and electronic device including the same.

Background Art

For example, flat panel display such as a liquid crystal display (LCD) or a light emitting diode (LED), the touch screen panel, solar cell, a transparent transistor of the electronic device includes a conductive thin film, the conductive film may be transparent. Used for the conductive thin film of the material can have, for example, in the visible light region is greater than or equal to about 80% of the light transmittance and is less than or equal to about 100 micro-ohm-cm (μΩ*cm) specific resistance. As to the conductive thin film can be used at present the oxide material comprises indium tin oxide (ITO), tin oxide (SnO₂), such as zinc oxide (ZnO). ITO as a result of indium flexible and shows the limited reserves and can cost is high. Therefore, the development of alternative materials desired. Furthermore, tin oxide and zinc oxide has a low conductivity and poor flexible.

In order to develop the next generation of electronic devices as being a cause for concern of a flexible electronic device (for example, bent or can be the electronic device is folded), need to be used for with high transparency and excellent flexibility and stability of the conductivity of the material of the transparent electrode of the development.

Content of the invention

One embodiment has a high conductivity and excellent optical transmittance of a flexible conductive film.

Another embodiment of the conductive film comprising said electronic device.

In one embodiment, the conductive film includes: by the chemical formula 1 and said compound having a layered crystal structure:

Chemical formula 1

MeCh₂

Wherein the Ru Me, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au, and Ch is sulfur, selenium, tellurium, or a combination thereof.

The conductive thin film at a temperature of less than or equal to 50 nm for a thickness of 550 nm wavelength light can have greater than or equal to about 80% transmittance.

By the chemical formula 1 compound can be expressed as b telluride compound.

By the chemical formula 1 can include a compound expressed PdTe₂, AgTe₂, IrTe₂, PtTe₂, AuTe₂, or a combination thereof.

In one embodiment, the conductive thin film is not including the surface oxide layer.

The conductive thin film can be a single crystal.

The conductive film can be greater than or equal to about 10,000 Siemens/cm conductivity of (S/cm).

Said compound can be display less than or equal to about 30 ohm/square of (Ω / square) (for example, in the 25 °C temperature) to the 550 nm wavelength light absorption coefficient (α) value of the product of the electrical resistivity (ρ).

The layered crystal structure belonging to the hexagonal and has a space group (Space number are allowed 164).

The conductive thin film can include a plurality of slice comprising said compound, and the stated nanometer plates can be electrically connected in contact with each other to provide.

The conductive thin film of the compound can comprise a continuous film. The continuous film can be formed by chemical vapor deposition.

Another embodiment offers electronic device, which comprises a conductive thin film, the conductive film includes a by the chemical formula 1 and said compound having a layered crystal structure:

Chemical formula 1

MeCh₂

Wherein the Ru Me, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au, and Ch is sulfur, selenium, tellurium, or a combination thereof.

The electronic device can be a flat panel display, the touch screen panel, solar battery, electronic windows (e-window), electrochromic mirror, hot mirror, a transparent transistor, or flexible display.

In one embodiment, as the metal disulfide of the compound represented by chemical formula 1 compound can be expressed with indium-tin oxide (ITO) is analogous to or than the conductivity of its large conductivity, and at the same time can be displayed in the visible light region of the light transmissivity of the in. Furthermore, the metal disulfide is a compound to be exfoliated layered material and can prepare for having enhanced a thin, flexible film. Furthermore, the compound of the metal disulfide with improved oxidation stability and so as to be capable of providing having substantially no surface oxide layer of the thin film.

Also disclosed a method of preparing conductive thin film, said method comprising: providing by the chemical formula 1 and said compound having a layered crystal structure:

Chemical formula 1

MeCh₂

Wherein the Ru Me, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au, and Ch is sulfur, selenium, tellurium, or a combination thereof; and the by the chemical formula 1 of a compound represented by the exfoliation in order to prepare the conductive thin film.

Description of drawings

By reference to the Figure a more detailed description of the disclosed exemplary embodiments of the content, the content of the above and other aspects, advantages and features will become more clear, wherein:

Figure 1 is the graph of relative intensity (arbitrary units) to the diffraction angle (two times θ that is, 2 the, degrees (°)) and by embodiment 1 preparation of PdTe₂ polycrystalline sintered body of the X-ray diffraction spectrum;

Figure 2 is the graph of relative intensity (arbitrary units) to the diffraction angle (two times θ that is, 2 the, degrees (°)) and by embodiment 1 preparation of PtTe₂ polycrystalline sintered body of the X-ray diffraction spectrum;

Figure 3A and 3B display embodiment 3 through in PtTe₂ polycrystalline sintered body of peeling of the mechanical exfoliation obtained of the sample of the results of transmission electron microscopy analysis;

Figure 4A-4C display embodiment 3 by of PtTe₂ polycrystalline sintered body peeling of the mechanical peeling of the sample obtained by energy dispersive X-ray spectrum of the result of the analysis, wherein the Figure 4A is the diagram of the scanning electron microscope (SEM) Image, diagram 4B for the chart 4A the position of the in 1, count to the energy (kilo-electron volts, keV) plan, and Figure 4C for the chart 4A the position of the in the 2, count to the energy (kilo-electron volts, keV);

Figure 5A and 5B to embodiment 4 by of PdTe₂ polycrystalline sintered body obtained by mechanical peeling peeling of the transmission electron microscope Image of the sample, wherein the Figure 5B is the enlarged view of the surface shown in Figure 5A, that the oxide layer does not exist;

Figure 6A-6E display the proportion 1 by in TiTe₂ polycrystalline sintered body obtained by mechanical peeling peeling of the transmission electron microscope analysis of the sample and the energy dispersion X-ray spectrum of the result of the analysis, wherein the diagram 6B-6D the 6A enlarged view of the indicated portion of, that exist in the polycrystalline layer; and

Figure 7 is the cross-sectional view of a conductive thin film comprising organic light-emitting diode of one embodiment of the device.

Mode of execution

And by reference to the following exemplary embodiments are attached to the Figure, the disclosed advantages and characteristics of the content and its realizing method will become clear. However, the present disclosure can be embodied many different forms and not be construed as limited to the invention in the embodiment of the; on the contrary, provides these embodiments so that this disclosure will be provided to the technicians of this field fully convey the scope of the invention. Therefore, in some embodiments, for the sake of clarity, no process and technology to male knowledge detailed description. If not further defined, in the specification of all terms (including technical and scientific terms) can be if the technicians of this field is usually defined as understand manner. Commonly used dictionary can be defined in terms of the idealized or magnified to explain, unless clearly defined. Furthermore, unless explicitly described to the contrary, the word "include" and variations such as "comprises" or "comprising" will be understood to imply that contains the states the essential factor, but it is not the exclusion of any other elements. Therefore, when used in this specification, terms "comprises" and/or "comprising", or "comprises" and/or "containing" indicating the presence of the stated features, regions, overall, steps, operations, elements and/or components (component), but does not preclude the presence or addition of one or more other features, regions, overall, steps, operations, elements, components (component), and/or set thereof.

Furthermore, singular includes the plural, unless otherwise mentioned. Therefore, in the singular form "a (a) (a, an)" and "(said) the" intention comprises a plurality of forms (including "at least one (a)"), unless the context clearly in addition specified.

On the drawings, for purposes of clarity, enlargement level, the thickness of the region. In the whole specification, the same mark the Figure represent the same element.

Will understand, when the one element for example level, film, region, or substrate is referred to as "in" other element when "on", it can be directly on the other element or the intermediate element can also be stored. On the contrary, when an element is referred to as "directly on" another element when "on", the intermediate element does not exist.

The terminology used herein is used for describing only the purpose of the specific embodiments, and is not intended as restrictive. "Or" means "and/or". As used herein, the term "and/or" including associated enumerated item of one or a plurality of arbitrary and all combined.

Furthermore, the present invention can be used in relative terms such as "lower" or "bottom" and "upper" or "top" to describe as illustrated in the and the other one of the elements of the relationship of the elements of. Will understand, in addition to the position of the as shown in the Figure outside, relative terms are intended to encompass different orientations of the device. For example, if the Figure of a turning device, described as the "lower" of other elements on the side of the element will be oriented in the other element of the "upper" side. Therefore, depending on the specific position, the exemplary term "lower" can encompass "lower" and "upper" two kind of position. Similarly, if the Figure of a turning device, described as "in" other element "lower" or "under" the element is of the "in" oriented "above" the other elements. Therefore, illustrative terms " in the... Below the "or" ... Under " can be covered in... Above and in... The two kind of position.

As used herein "about" or "approximately" includes the values and means that in such as by one of ordinary skill in the art taking into account the measuring and the discussion of the error of the measurement on the concrete quantity (i.e., limit of the measurement system) for the determined value of the acceptable deviation range. For example, "about" can mean that in the presence of one or more within the range of the standard deviation.

With reference to in this text as idealised embodiment schematic view of the cross-sectional view of an exemplary embodiment is described. In this way, is made of, for example, it is expected that the manufacturing techniques and/or tolerances of the shape of the graphical representation of the deviation of the. Therefore, the embodiment described herein should not be construed as limited to such as the area of the representation in this specific form, but includes for example, for producing lead to the deviation of the shape. For example, graphic or described as flat region may be typically has a rough and/or nonlinear features. Furthermore, the illustrated acute angle can be circular. Therefore, as shown in the Figure is the area of the of the illustrative in nature, and their shapes are not intended to show the exact shape of the region, and is not intended to limit the scope of the claim.

In one embodiment, the conductive film includes a by the chemical formula 1 and said compound having a layered crystal structure:

Chemical formula 1

MeCh₂

Wherein the Ru Me, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au, and Ch is sulfur, selenium, tellurium, or a combination thereof.

Said compound can be for two telluride compound, and hence Ch can be tellurous. The compounds can include PdTe₂, AgTe₂, IrTe₂, PtTe₂, AuTe₂, or a combination thereof. In one embodiment, the conductive film is substantially free of surface oxide layer. For example, the conductive film includes a by the chemical formula 1 and having a layered crystal structure of that of the slice of the compound, wherein the nanometer disc does not contain the surface oxide layer. The conductive film may include monocrystalline compound, polycrystalline compound, or a combination thereof.

In one embodiment, the conductive thin film can have high conductivity level of high light transmittance and, and thus can be advantageously used for great importance to high electrical conductivity and high transparency of the application (for example, transparent electrode). For example, the conductive thin film at a temperature of less than or equal to 50 nm in thickness of 550 nanometer (nm) with light at a wavelength of greater than or equal to about 80%, for example greater than or equal to about 85%, or greater than or equal to about 90%, about 80% to about 99%, or about 85% to about 98% of the light transmittance. With such a high light transmittance level together, the conductive thin film can have a relatively high conductivity level, for example, greater than or equal to about 10,000 (S/cm) Siemens/cm, about 1×10⁴ S/cm-about 1×10⁶ S/cm, or about 5×10⁴ S/cm-about 5×10⁵ S/cm conductivity.

The compound of the transition metal disulfide (hereinafter also called the TMDC) can have the conductivity is the conductivity of the semiconductor, but they are recognized as non-transparent material, therefore, has only a little attempt to use them as a transparent conductive film. For example, in the visible light region are caused to exhibit high transmittance of a transition metal of a very thin silicide film on the second which (has a thickness of several nanometers) attempt. However, the transition metal b which tend to compound via the exfoliation process for preparing the nano-piece is easy to oxidize. Therefore, electrical properties of the resulting material can be negative and drastically reduced. Therefore, even if the transition metal disulfide slice of the compound can be formed, also has been difficult to obtain a metal b which the transition of the transparent conductive thin film. On the contrary, comprises having a layered crystal structure of the chemical formula 1 is a compound of a compound of sulfur can be slice with the other transition metal disulfide compound is compound compared with the oxidation stability is greatly enhanced, and hence can have improved exfoliation nature and could be used to prepare nanometer without significant oxidation. Therefore, according to one embodiment, the preparation of the conductive thin film does not contain or not significantly includes (or internal) surface of the oxide layer. In one embodiment, based on the total weight of the conductive thin film, the conductive thin film of the oxide content can be less than about 2 weight %, such as less than about 1 weight %, less than about 0.1 weight %, of from about 0.001 weight percent (weight %) to about 2 weight %, about 0.005 weight % to about 1% by weight, or about 0.01 weight % to about 0.1 weight %.

In one embodiment, the conductive film can be greater than or equal to about 4000S/cm for example greater than or equal to about 5000S/cm, greater than or equal to about 6000S/cm, greater than or equal to about 7000S/cm, greater than or equal to about 10,000 S/c m, or even greater than or equal to about 30,000 S/c m, or about 4×10³ S/cm-about 1×10⁶ S/cm, or about 8×10⁴ S/cm-about 5×10⁵ S/cm relatively high conductivity level.

In order to the development of improved conductivity and is transparent in the visible light range of a flexible transparent electrode material, a variety of efforts have been carried out. Metal can have a high electron density and high conductivity. However, most of the metal tends to the reaction of the oxygen in the air to form the oxide on the surface of contact with air and hence the of greatly reducing the conductivity. Furthermore, the advantages of good electric conductivity and shown to reduce surface oxidation of the surface of the ceramic material to reduce the contact resistance. However, currently available electrically conductive ceramic material (such as ITO) has the stable supply of the raw material difficult. Furthermore, they may be unable to provide the metal conductivity considerable conductivity and their flexible is often poor.

On the contrary, the disclosed comprises a formula 1 compound provides a high conductive thin film of the conductivity and high transparency and high oxidation stability level. Furthermore, chemical formula 1 compound having a layered crystal structure. In this structure, the unit structure are connected to each other by van der Waals force and therefore the sliding between may experience layer, and flaking off of the liquid phase by mechanical peel off or the nano sheet for their preparation. Therefore, some embodiments can provide conductive thin film of flexible electronic device suitable for the application of the improvement of the flexible horizontal.

Chemical formula 1 compound can be with less than or equal to about 30 ohms/square (Ω / square) in the 25 °C to the 550 nm wavelength light absorption coefficient (α) value of the product of the electrical resistivity (ρ). The absorption coefficient and resistivity can be obtained by the computer simulation. Resistivity (ρ) through the corresponding rare earth element chalkogenide the crystal of the compound near the Fermi energy level structure, calculate the energy band (band, band) structure and density of states obtained (DOS). Furthermore, for a given wavelength the absorption coefficient (α) of the dielectric constant can be calculated from the compound, through the application of the dielectric constant is the Drude model and consider because of interband transitions obtained by electronic transitions. For providing the absorption coefficient (α) and the electrical resistivity (ρ) of the analog method, may further refer to ViennaAb-initioSimulationPackage (by GeorgKresse and JurgenFurthmuller prepared, InstitutfurMaterialphysik, UniversitatWien, Sensengasse8, A -1130Wien, Austria, 2005 years 8 month 24 day, http://cms.mpi.univie.ac.at/VASP /), will all its introduction as a reference herein. The simulation program are summarized in table 1 in.

Table 1

In table 1 in, the use of the following abbreviations:

DFT: density functional theory;

DFPT: density functional infinitesimal disturbance theory;

Drude model: used for solid free electron model;

σ, τ, m_eff,_μ, ρ: conductivity, relaxation time, effective mass, mobility, resistivity.

In the below, more detailed ming Biao to said 1 description.

In order to calculate the material of the quantum mechanical state, based on density functional theory (DFT) method (through the use of an electronic density function replace the wavefunctions to describe electronic distribution but solves method of quantum mechanics equation) to calculate the primary principle (by basic equation without use of external parameters of the calculation carried out under condition) in order to calculate the electronic quantum mechanical state. Using VASP (ViennaAbinitiosimulationpackage code, the code for the primary principle DFT) electronic state is calculated. From InorganicCrystalStructureDatabase (ICSD) choose to include the two-dimensional electron gas (2DEG) layer of candidate material. The atomic structure of input candidate material through the analog information and electronic energy level can be calculated, and for such electronic, the electronic calculation of the-space k density of states function and energy density function.

Computer simulation calculated by the DFT electronic structure provides E-k diagram (with structure can be) and DOS (state density: electronic state density, each can is the density function of the electronic state of) information, so that the material can be determined is the metallic conductive material (DOS (E_F) > 0) also is a semiconductor material (DOS (E_F) =0), the electronic can be used depends on the maximum level (E_F) on the existence of the DOS.

In order to predict the electrical conductivity of the metallic conductive material (σ), by introducing a semi-classical Boltzmann transport model and estimate its conductive characteristics. In this case, it is assumed that the electronic relaxation time (τ: in its period, the electronic can move without the duration of the collision) is a constant (refer to N.W.Ashcroft and N.D.Mermin, SolidStatePhysics, Holt, RinehartandWinston, 1976, the contents are introduced as a reference herein).

Boltzmann transport

σ=(e2/4π3)τ[!Integral!]dkv(k)v(k)(-∂f/∂E)

Here, the electronic relaxation time τ, k k-space in the state of electrons in the, v (k) to the speed of the electronic state k, f is a Fermi-Dirac distribution function, and E as energy. In this case, v (k) can be calculated from Figure E-k, and σ / τ can be obtained from the above formula.

Decision transmitted and absorbed of the conductive material can include the mechanism of the free electrons of the plasma-shaped oscillation caused by absorption and because with the electronic-with transition taken to the belt caused by the absorption. Through the as shown in table 2 are taken into account of the method of in the mechanism of each of the analog method for quantum computing (refer to N.W.Ashcroft and N.D.Mermin, SolidStatePhysics, Holt, RinehartandWinston, 1976).

Table 2 the [...] to the optical nature of the analog watch

Here, B said band, and said D Drude model.

In this case, the solid dielectric constant (ε), refractive index (n) and the absorption coefficient (α) is as follows is shown the relationship between. The dielectric constant, the transitions should be considered part of the belt (ε_(band)) and and the transition part of the concerned (ε_(Drude)) the two.

ε (ω) =ε_(Drude) + ε_{( band)}

= ε₁ (ω) +iε₂ (ω) dielectric function

(n+ik)² =ε (ω) refraction function

Absorption coefficient α (ω) =4 πk / λ

If in the above conductivity is calculated, as described, can be absorbed by the pre-calculated between the band structure calculation, caused by free electrons in-band absorption is as the following based on the modeling Drude conductivity and optical coefficient of the analog computation of the calculated (refer to JinwoongKim, JournalofAppliedPhysics110,0835012011, its contents are introduced as a reference herein).

CGS units

σ (ω) =σ₀ / [1-iωτ] AC conductivity

σ₀ =ne² τ / mDC conductivity

Ε (ω) =1 +i (4π / ω) σ (ω)

ω_p² τ=σ₀ / ε₀ (si)

= 4 πσ₀ (cgs)

ε (ω) =1 +i (4π / ω) σ₀ / [1-iωτ] =1 - (4 πσ₀ / ω) / [i+ωτ]

= 1 - (4 πσ₀ / ω) (-i+ωτ) / [1 + (ωτ)²]

= 1 - (ω_p τ)² / [1 + (ωτ)²]

+i (ω_p τ)² / [1 + (ωτ)²]

[!Element!]1=1-ωp2τ21+ω2τ2n=12([!Element!]1+([!Element!]12+[!Element!]22)1/2)1/2[!Element!]2=ωp2τ2τω(1+ω2τ2)κ=12(-[!Element!]1+([!Element!]12+[!Element!]22)1/2)1/2

Ω: frequency

ω_p: plasma frequency

K: extinction coefficient

In this way, belt with the absorbed and can be calculated by the calculation of the dielectric function of the material, and can be formed by this analog its optical constant. Finally, the material can be calculated from the refractive index of the (R), the absorption coefficient (α), and the transmissivity (T).

According to the aforesaid method, a plurality of metal two sulfur belonging to the absorption coefficient (α) of the product of the electrical resistivity (ρ) is collected in the table 3 in.

Table 3

According to the equation, resistivity (ρ) the product of the absorption coefficient (α) can be expressed sheet resistance (R_s) with the product of (-lnT), wherein T said transmissivity. Therefore, as to the conductive thin film material, has relatively low value of ρ *α the compounds of the may be favourable.

e^-αt =T (in other words, αt=-lnT)

R_s =ρ / t

∴ρ*α=R_s * (-lnT)

Α: absorption coefficient

Ρ: resistivity

T: transmissivity (in λ =550nm is)

T: thickness

R_s: sheet resistance

According to the embodiment of a conductive thin film comprises the compound can have less than or equal to about 30, for example, less than or equal to about 20, or about 1-about 30, or about 2-about 25 and the resistivity of the product of the absorption coefficient (in other words, R_s * (-lnT)), to provide a high conductivity and excellent clarity (i.e., low sheet resistance and high light transmittance) of the conductive thin film.

According to one embodiment including a conductive thin film of metal (i.e., Ru, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au) and non-metallic elements (i.e., sulfur, selenium, tellurium, or a combination thereof) and even if the inorganic material under the thin the thickness of the can also be provided with a very high conductivity. Wishing to be bound by any specific theory-tethered, that, because of the above-mentioned conductive film included in the layered crystalline structure of the two-dimensional limited electronic, and even with a small thickness of the very thin electronic in the membrane states movement can also be high mobility, therefore, the conductive film can be a very high conductivity and high transparency.

Furthermore, the compounds having a layered crystal structure of the conductive thin film may experience interlaminar sliding to provide improved flexible. According to one embodiment, are represented by chemical formula 1 the compound of the rare earth chalcogenides can be layered crystal structure belonging to the space group (Space number are allowed 164) of the six-party system.

According to one embodiment, the conductive film can be through the following preparation: ready to chemical formula 1 is a compound of the metal disulfide compound raw material, by its preparation of polycrystalline or single-crystal bulk material, or by the powder of the material to obtain the tile; and using the raw material, preparation of the bulk material, or its powder with appropriate method such as vapor deposition, and the like, in order to form the conductive thin film (for example, a transparent conductive layer). Alternatively, the conductive film can be through the following obtain: the powder of the block material to provide a nanometer of peeling off of the liquid phase, and the obtained nano sheet into thin film.

The metal disulfide compound is compound may include the raw material of the element or compound containing the element. For example, the raw material may include elemental Ru, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au, or includes Ru, Os, Re, Rh, Ir, Pd, Pt, cu, Ag, or Au compound. For example, the raw material may include sulfur, selenium, tellurium, or a combination thereof. According to one embodiment, the raw material can be a metal with sulfur, selenium, tellurium, or the combination of the compounds.

A polycrystalline bulk material can be by the above-mentioned raw materials quartz ampoule method, arc melting method, and the solid-state reaction method. For example, a quartz ampoule method comprises the raw materials introduced into the quartz tube or in the ampoule made of metal, the seal under the vacuum, and to be heated in order to carry out the solid phase reaction or melting process. Arc melting method including element to introduce the raw materials to the chamber, in an inert gas (for example, nitrogen gas, such as argon gas) arc discharge process is conducted under an atmosphere of elements in order to make the raw material melt, and make its solidification. Solid-state reaction method can include raw material powder is mixed; the resulting mixture is then heat-treated and pelleting, or its heat treatment and then granulating; and finally, the prepared by the sintering of the granular material.

The obtained polycrystalline bulk material may experience sintering process in order to produce highly densified product. The height for the densification of the product can be used as a sample for measuring electrical conductivity. Such a densification process can be through hot-press method, spark plasma sintering method, such as method of hot forging. The hot-press method comprises the applied to the powdered compound in a mould with a predetermined shape, and the example as promised 300 °C-about 800 °C in example as promised under the high temperature of 1 MPa (MPa) to about 300 megapascals (MPa) (for example, 30 MPa to about 300 MPa) high pressure forming. The spark plasma sintering method comprises the powdered compound exert under the pressure of the high voltage current, for example, at about 30 MPa to about 300 MPa is applied under the pressure of about 50 amps (A)-about 500A current, in order to the material sintered within a short time. The hot forging method can include powder compound in example as promised 300 °C-about 700 °C compression and under the high temperature of sintering.

The single crystal material can be obtained by adoption of the following: the preparation through the single crystal ingot growth. states the ingot can be obtained by adoption of the following : (congruent) the phase of the molten material is heated to higher than the temperature of the melting point of said material, and then the slow cooling. For example, the raw material can be in the mixture is introduced to the quartz ampoule, the ampoule under the vacuum of the seal, the raw material mixture is melted, and then the molten mixture is slowly cooled in order to offer the crystal ingot. By selecting the cooling speed of the molten mixture of selected grain size. The growth of the single crystal can be through the metal flux method, Bridgman method, optical floating zone method, such as vapor transmission method (vaportransport). Metal flux method comprises the following method: the raw material powder in the crucible, together with the additional flux of molten under the high temperature, and a slow cooling to crystal growth at a predetermined temperature. The Bridgman method includes introducing elements of raw material in the crucible and connect its under the high temperature of the crucible heating until the element at the end of melting the raw material, and then the high-temperature region and moving slowly in the sample is partially melted by the temperature of the whole sample, to grow a crystal. Optical floating zone method comprises the following method: the element forming in the raw material and the feed rod seed crystalbar (feedrod) (seedrod), through the light is focused on the feed bar and make the sample in the partial melt under the high temperature, and the molten part of the slowly upward to grow a crystal. Vapor transmission method comprises the raw materials introduced into the elements in the bottom portion of the quartz tube, and the heating elements of the raw material, and the upper portion of the the states the quartz tube maintained in a low temperature, in order to use the raw material of the evaporation in the low temperature element and performing solid phase reaction to thereby grow a crystal. The obtained single crystal material can be according to the conductivity of DC4-terminal method for measuring.

Obtained can be polycrystalline or single crystal bulk material crushing to provide crystalline powder. The crushing can be by any suitable method, for example, ball milling for, without special restriction. After the crushing, using, for example, the screen can be provided with a powder of uniform size.

Obtained by use of polycrystalline or single-crystal bulk material target and so on as vapor deposition, including the compound to provide a thin continuous film (i.e., the conductive thin film). The gas is deposited by a physical vapor deposition method, for example, thermal evaporation, sputtering, chemical vapor deposition (CVD), atomic layer deposition (ALD), or pulsed laser deposition. The deposition can use any suitable known or commercial apparatus. Deposition conditions and the deposition method of the compound of the type of change, however, there is no special restriction.

According to another embodiment, the bulk material of the above compounds or its powder experience peel off of the liquid phase so as to provide a plurality of nanometer, then the plurality of nano-piece to provide contact is electrically connected with each other, thereby providing a conductive thin film.

In peeling off the liquid phase, which can lead the bulk material or the powder of the ultrasonic treatment in a suitable solvent. Suitable for use in the embodiment of the peeling off of the liquid phase of the solvent may include, but are not limited to, water, alcohol (e.g., isopropanol, ethanol, or methanol), N-methyl pyrrolidone (NMP), hexane, benzene, dichlorobenzene, toluene, chloroform, diethyl ether, dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EtOAc), acetone, dimethyl formamide (DMF), acetonitrile (MeCN), dimethyl sulfoxide (DMSO), ethylene carbonate, propylene carbonate, γ-butyrolactone, γ-valerolactone, perfluorinated aromatic solvent (for example, hexafluorobenzene, eight fluorine toluene, five fluorine animal pen nitrile, and five fluoro pyridine). Including the above-mentioned solvent can be used in combination of at least two kinds.

The solvent can further include additives such as a surfactant to promote exfoliation and prevent spalling agglomeration of slice. Examples of the surface active agent can include sodium dodecyl sulphate (SDS) and sodium dodecyl benzene sulfonate (SDBS).

The ultrasonic treatment can use any appropriate can be obtained of the ultrasonic processing apparatus for, and the same conditions (for example, ultrasonic processing time) is not particularly restricted, but considering the used solvent and in the solvent and properly selecting the powder concentration. For example, the ultrasonic treatment can be greater than or equal to about 1 hour, for example, about 1 hour to about 100 hours, but is not limited to this. The powder concentration in the solvent can be greater than or equal to about 0.01 g/ml (g/mL), for example, in about 0.01g/mL-about 1 g/l in the range of, but not limited to this.

In order to promote exfoliation, can make the lithium atom is imbedded to the stated compound having a layered crystal structure in the. According to one embodiment, the the compound is included in the aliphatic hydrocarbon solvent such as hexane, alkyl lithium compounds of the (for example, C2-C8 alkyl lithium compounds are, for example, composite material) contact with a solution of, for example, in impregnated in the solution, in order to make the lithium atoms in the compound is imbedded to the stated, and experience product obtained by ultrasonic treatment in order to provide a plurality of slice comprising said compound. For example, the product obtained thereby is placed in water, water and the embedded in the lithium ion can react between layers of the crystal structure to produce hydrogen, thus speeding up the interlaminar separation. The obtained nano-sheet according to the appropriate method (for example, centrifugal) the separation and washing thereof.

states a nanometer piece in including the (for example, a nanometer thin slice) in the conductive thin film, said m physical contact with each other in order to provide electrical connection. When the nanometer physical contact in order to form the thin film, the prepared film can provide enhanced transmittance. No special restrictions the length of the slice, and can be appropriately chosen. For example, the nanometer sheet can have less than or equal to about 500 µm example of about 10 nm to about 500 µm, or about 20 nm to about 50 µm, about 10 nm-about 10 µm length of, but is not limited to this. The stated nanometer sheet can have less than or equal to about 100 nm, about 1 nm to about 100 nm, or about 2 nm to about 80 nm thickness, but is not limited to this. The film obtained can have greater than or equal to about 50%, about 50% - 100%, or about 55% to about 98% coverage, is set up in the membrane-based on the total area of the substrate. The film obtained in the thickness of less than or equal to about 20 nm, such as less than or equal to about 5 nm, about 1 nm to about 50 nm, or about 2 nm to about 40 nm in the 550 nm wavelength light can have a high transmittance, for example, greater than or equal to about 80%, or greater than or equal to about 85%, or about 80% - 100%, or about 85% to about 98% of the transmissivity. In one embodiment, the thickness of the conductive thin film may be about 1 nm to about 50 nm, about 2 nm to about 40 nm, or about 3 nm to about 30 nm. The conductive thin film can have about 0.01 giga Pascal (GPa)-about 10GPa, about 0.05GPa-about 8GPa, about 0.1GPa-about 6GPa, or about 0.5GPa-about 4GPa is the Young's modulus of the tensile modulus. Moreover, the conductive membrane is the after bending (bending) can keep its conductive nature. For example, when mounted on a suitable substrate, for example, polyethylene glycol terephthalate is ester on the bottom, through the DC (constant current) when measuring four probe method, the conductive thin film around the with 10 mm diameter the stick is curving of 180° with the conductivity after: the former is in bending the same about the conductivity of 80% - 100%, about 85% to about 99%, or about 90% to about 98%.

Using the nanometer sheet film-forming can be carried out by any suitable method. For example, the form of the film can be formed by printing after ink or paste, spraying, dip-coating, and the like.

According to one embodiment, the manufacturing of the slice of contact with de-ionized water, for example is added to the deionized water, and the resulting dispersion again ultrasonic processing. Dispersion by the ultrasonic processing to add different water miscible organic solvent (for example, an aromatic hydrocarbon such as xylene or toluene). When the shaking when the mixture is obtained from this, in the water and organic solvent is formed at the interface between the film including nano-piece. When the clean, the wetted, and from a glass substrate of the plasma treatment (dip) gently sinking and out to the interface, the including nanometer slice in the thin film on the interface on the substrate. Can be controlled by the in the water/organic solvent on the surface of the concentration of the each area of the slice of the substrate and including the nanometer piece from a mixture of the speed/angle when the selected thickness of the film.

The conductive thin film has high conductivity, enhanced light transmittance, and excellent flexibility, and therefore can replace comprises a transparent conductive oxide such as ITO, ZnO and the like including the electrode of the nanowire Ag and the transparent film.

Another embodiment of the conductive thin film comprising the above electronic device. The electronic device comprises a of the conductive film can be and are the same as those disclosed above. The electronic device can include, for example, flat panel display (e.g., LCD, LED, or OLED), the touch screen panel, solar battery, electronic windows, hot mirror, a transparent transistor, or a flexible display, but is not limited to this.

Figure 7 is the cross-sectional view of a conductive thin film comprising organic light-emitting diode of one embodiment of the device.

According to one embodiment of the organic light emitting diode device includes a substrate 10, the lower electrode 20, the face of the lower electrode 20 of the upper electrode 40, and is interposed between the lower electrode 20 and the upper electrode 40 of emitting layer between the 30.

Substrate 10 can include inorganic materials such as glass, or organic material such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polynaphthalic acid terephthalate, polyamide, polyether sulfone, or a combination thereof, or silicon wafer. Including the above-mentioned substrate can be the use of a combination of at least two kinds.

The lower electrode 20 and the upper electrode 40 as the cathode and the other one of the anode. For example, the lower electrode 20 can be a and anode the upper electrode 40 can be a cathode.

The lower electrode 20 and the upper electrode 40 is at least one of the transparent electrode. When the electrode 20 is a transparent electrode, the organic light emitting diode device can be provided with a bottom emission structure, wherein towards the substrate alone 10 transmitted; and when the upper electrode 40 is a transparent electrode, the organic light emitting diode device can have a top-emitting structure, wherein the light is far away from the substrate 10 a. Furthermore, when the electrode 20 and the upper electrode 40 both are transparent electrode, light towards the substrate 10 and away from the substrate 10 emission.

The transparent electrode can be including the above-mentioned conductive film. The conductive thin film with the same as described above. The conductive thin film can have a high electron density. The conductive thin film can be used for replacing LiF/Al or MgAg alloy.

Emitting layer 30 can include transmitting primary color such as red, green, blue, and the like of the organic material, or inorganic material and the mixture of the organic material, said organic material such as polyfluorenes derivatives, plurality of poly-P-phenylene phenylmethylidene vinyl derivatives, polyphenylene derivatives, polyvinyl carbazole or its derivatives, poly-thiophene derivatives, these polymeric materials or a perylene-based pigment, based on coumarin pigment, rhodamine-based pigment, rubrene, perylene, 9,10- diphenyl anthracene, four phenyl butadiene, nero is red, coumarin, quinacridone, the compounds of the preparation. By the organic light-emitting diode device the primary color of the emitting layer of the combined display desirable space of the Image.

Emitting layer 30 can be through the primary color (for example red, green and blue the three primary colors) combined and emitting white light, and in this case, the color combination can be the color of the adjacent pixel by the combined or laminated in the vertical direction of the emission of white light combination.

The emitting layer 30 and the upper electrode 40 layer is arranged between 50 in order to improve the emitting layer 30 of the light-emitting efficiency. In this Figure, auxiliary layer 50 only display the reflective layer 30 and the upper electrode 40 between, but it is not limited to this. The emitting layer 30 and the lower electrode 20 between, or the reflective layer 30 and the upper electrode 40 and between the reflective layer 30 and the lower electrode 20 is arranged between auxiliary layer 50.

Auxiliary layer 50 may include electronic and cavity for the balance between the electron transport layer (ETL) and a hole transport layer (HTL), for enhancing the injection of electrons and holes (EIL) the electron injection layer, a hole injection layer (HIL), and the like. It can include one or more from the selected layer.

Has been made clear that the conductive thin film is applied to the organic light emitting diode device of the embodiment. Moreover, the conductive thin film can be used as a transparent electrode including the electrode of the electronic device without special restrictions on, for example, by acting on the picture element electrode of the liquid crystal display (LCD) and/or common electrode, for organic light-emitting diode device of the anode and/or cathode, is used for the plasma display device of the display electrode, and is used for the touch screen panel device of the transparent electrode.

In the below, the implementation of example detail with reference to embodiments. However, these embodiments would never be interpreted to limit the scope of the present disclosure.

Embodiment

Embodiment 1: preparation of polycrystalline sintered body

Preparation by the following way polycrystalline sintered body.

In the glove box, the gold (Au), palladium (Pd), or platinum (Pt) (purity: 99.9%, manufacturer: & DKoreaCo. R, Ltd.) respectively with simple substance tellurium (purity: 99.99%, manufacturer: & DKoreaCo. R, Ltd.) to 1:2 molar ratio of mixed to provide a binary mixture. The prepared mixture is introduced to the quartz glass tube, and the tube under the vacuum seal. The quartz glass tube is introduced into the box-type furnace and to 100 degree Celsius/hour (°C/h) are respectively heated up to the heating rate 800 °C (to gold mixture and palladium mixture), or 1200 °C ( regarding platinum mixture), the same temperature and maintain the 1 day and by a slow cooling to room temperature (solid state method).

The obtained sample crushing and using the SPS apparatus (by FujiElectronicIndustrialCo., Ltd. Manufacturing, type name: Dr.Sinter) in 600 °C the temperature of the 70 MPa the under the pressure of the process of spark plasma sintering (SPS).

The sintered body obtained, using ULVAC-RikoZEM-3 device according to DC4 terminal method at room temperature/atmospheric condition measuring electrical conductivity, and the result is collected in the table 4 in.

For two telluriumplatinum fevertwo telluriumarrowhead fever sintered body and each of the sintered body, to X-ray diffraction analysis and the results shown in Figure 1 and Figure 2 in. Figure 1 results confirmed PdTe₂ sintered body includes has hexagonal and has a space group (164) two tellurium arrowheads layered crystal structure. Figure 2 results confirmed, PtTe₂ sintered body includes has hexagonal and has a space group (164) two tellurium platinum layered crystal structure.

Table 4

Table 4 results confirmed that, according to this embodiment of the compound of compound which has high conductivity.

Embodiment 2: preparation of single crystal

In the glove box, palladium (purity: 99.99%, manufacturer: & DKoreaCo. R, Ltd.) or platinum (purity: 99.99%, manufacturer: & DKoreaCo. R, Ltd.) respectively with simple substance tellurium (purity: 99.99%, manufacturer: & DKoreaCo. R, Ltd.) to 1:2 molar ratio of mixed to provide a binary mixture. The prepared mixture is introduced to the quartz glass tube, and the tube seal under the vacuum condition. The quartz glass tube and placed in the box-type furnace 100 °C/h heated to the rate of 750 °C (for palladium mixture) or 1150 °C ( regarding platinum mixture), and in this temperature for about 1 hour to about 5 hours. Furthermore, the temperature of the molten product to about 1 °C/h -2 °C/h rate reduced to 550 °C (for palladium mixture) or reduced to 950 °C ( regarding platinum mixture) to grow a large crystal grain size of the crystal ingot. The growth of the ingot by cooling to room temperature.

Using ULVAC-RikoZEM-3 room temperature/atmospheric conditions in the equipment under DC4 terminal method for measuring the conductivity of the obtained single crystal of, and the result is collected in the table 4 in. Results confirmed that, the electrical conductivity of the single crystal than the corresponding conductivity of the polycrystalline sintered body is slightly high.

Embodiment 3: PtTe₂ microcarcinoma sheet and its preparation of (Microflake) TEM-EDS analysis

According to such K.S.Novoselov, "ElectricFieldEffectinAtomicallyThinCarbonFilms", ScienceVol. 306, p.666 (2004) (its content as a reference herein all introduced) use of the method of in 3MScotch embodiment of adhesive tape (tape) will be 1 obtained PtTe₂ sintered body is mechanically peeled off in order to obtain with 100 nm of the thickness of the micro-sheet.

The use of transmission electron microscope (TECNAIF30U-TWIN) (TEM), for analysis and TEM energy dispersion X-ray spectroscopy, and the result shown in chart 3A and 3B and Figure 4A-4C in. Figure 3A and 3B and Figure 4A-4C results confirmed that, in PtTe₂ spalling oxide layer does not exist in the sample.

Figure 4A the position of the in 1 the energy dispersion X-ray analysis to confirm the content of Pt 45.5 atomic percent (atomic %) and Te content is 54.5 atomic %. Figure 4A the position of the in the 2 energy dispersion X-ray analysis to confirm the content of Pt 47.8 atom % and the content of Te 52.2 atomic %.

Embodiment 4: PdTe₂ microcarcinoma sheet preparation and its TEM-EDS analysis

With the embodiment 3 in the same manner as outlined in using 3MScotch by the embodiment of the adhesive tape 1 obtained PdTe₂ sintered body is mechanically peeled off in order to obtain with 100 nm of the thickness of the micro-sheet. The use of transmission electron microscope (from TECNAIF30U-TWIN) (TEM), obtained on this analysis TEM peeling of the samples, and the result shown in chart 5A and 5B in. Figure 5A and 5B results confirmed that, in PdTe₂ spalling oxide layer does not exist in the sample.

The proportion 1: TiTe₂ microcarcinoma sheet preparation and its TEM-EDS analysis

As follows from in addition, with the embodiment 1 in the same manner as outlined in the obtain TiTe₂ sintered body: using titanium as the metal element. With the embodiment 3 in the same manner as outlined in using 3MScotch adhesive tape prepared by this TiTe₂ sintered body is mechanically peeled off in order to obtain with 100 nm of the thickness of the nano sheet. The use of transmission electron microscope (from TECNAIF30U-TWIN) (TEM), obtained on this analysis TEM peeling of the samples, and the result shown in chart 6A-6E in. Figure 6A-6E results confirmed, TiTe₂ exfoliation sample comprises less than about 10 nm of the thickness of an amorphous layer, it is considered to be natural oxide layer. Energy dispersion analysis table 5 provides the results of the in.

Table 5. Figure 6A point in P1-P4 analysis

Embodiment 5: PdTe₂ thin film manufacturing

The embodiment of using the 1 preparation of PdTe₂ as a sintered body using and target Nd/YAG laser (device) under the following conditions in Al₂ O₃ substrate pulse laser deposition (PLD).

PLD apparatus: PLD5000DepositionSystems, PVDProducts

Output power: 60mJ/cm²

Time: 20 minutes

Substrate temperature: 600 °C

Vacuum: 2*10^-6 Pa

The obtained PdTe₂ deposition film has about 20 nm thickness.

Embodiment 6: including PdTe₂ slice of the manufacture of the film

By the embodiment 1 of the preparing PdTe₂ sintered body crushing and the 0.1 g (g) the obtained powder is dispersed in 100 ml including dissolved in the hexane in the efficient, and the resulting dispersion mixing 72 hours. Furthermore, the powder is taken out from the dispersion and using hexane washing, and drying in the argon atmosphere in order to obtain the lithium is inserted into the (embedded) PdTe₂ powder. In the glove box of the lithium is inserted PdTe₂ powder is put into a small bottle, then adding a predetermined amount of water and the resulting mixture undergoing ultrasonic processing 1 hour. As the generation of hydrogen, to provide an interlayer separation occurs PdTe₂ nano sheet.

The obtained slice of the centrifugal, and then the precipitate is washed with water and again centrifugal.

The obtained slice of the vial and precipitate by adding 3 ml deionized water and the ultrasonic treatment. Adding 2-3mL toluene, to the vial to stir and in the layer and the interface between the toluene layer comprises nano-piece provided at the film. From plasma processing of the glass substrate is gently sinks to the interface and pull it up, the surface is present in the said including PdTe₂ sprawls slice of the film on the glass substrate.

Although it has been the practice at present is considered to be the content of an exemplary embodiment of the disclosure are described, but it will be understood, the invention is not limited to the disclosed embodiment, but on the contrary, the intention in the accompanying claims include the spirit and scope of the in the various modifications and equivalent arrangement.