WO2011007925A1 - Hole transporting layer for light emitting devices and solar cells and method for manufacturing the same - Google Patents
Hole transporting layer for light emitting devices and solar cells and method for manufacturing the same Download PDFInfo
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- WO2011007925A1 WO2011007925A1 PCT/KR2009/005309 KR2009005309W WO2011007925A1 WO 2011007925 A1 WO2011007925 A1 WO 2011007925A1 KR 2009005309 W KR2009005309 W KR 2009005309W WO 2011007925 A1 WO2011007925 A1 WO 2011007925A1
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- Prior art keywords
- hole transporting
- transporting layer
- thin film
- conductive thin
- light emitting
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000010409 thin film Substances 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 16
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000012495 reaction gas Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 230000003746 surface roughness Effects 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004054 semiconductor nanocrystal Substances 0.000 description 4
- 229910001080 W alloy Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
Definitions
- the present disclosure relates to a hole transporting layer for light emitting devices and solar cells and a method for manufacturing the same.
- light emitting devices using semiconductor nanocrystals or puantum-dots have advantages of self-luminescence and low power consumption, as well as can realize color reproduction of high purity, high brightness, and high efficiency by quantum confinement effects due to the semiconductor nanocrystals with particle size of about several nanometers.
- the light emitting devices using semiconductor nanocrystals are considered as the next-generation electro-optical device.
- Such a light emitting device has a structure similar to that of a solar cell.
- the light emitting device includes a substrate, a transparent electrode, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electrode.
- the solar cell includes a substrate, a transparent electrode, a hole transporting layer, a light absorbing layer, an electron transporting layer, and an electrode.
- the transparent electrode of the light emitting device and solar cell serves as an electrode and transmits light.
- ITO indium tin oxide
- the ITO film should have a thick thickness to realize low resistivity.
- the ITO film gets thicker, light transmittance thereof is low.
- the ITO film is used as the conductive thin film of the light emitting device.
- indium (In) used as a raw material of the ITO film is a rare metal having limited reserves, the light emitting device and the solar cell gradually increase in price.
- the hole transporting layer is necessary for effectively transporting holes to the light emitting layer. Also, the hole transporting layer having proper hole concentration and electrical conductivity according to characteristics of the light emitting layer is required. Thus, the hole transporting layer should have a thin thickness in order to have proper hole concentration and electrical conductivity and transmit a large amount of light.
- Embodiments provide a hole transporting layer for light emitting devices and solar cells, in which a substrate and an electrode that are essential component parts of the light emitting device or the solar cell are replaced with a flexible metal substrate, and a surface of the metal substrate is oxidized or deposited to form the hole transporting layer and a method for manufacturing the same.
- a hole transporting layer for a light emitting device and a solar cell is characterized in that the hole transporting layer is formed of nickel oxide (NiO) formed by oxidizing a side of a conductive thin film formed of a flexible metal.
- NiO nickel oxide
- a hole transporting layer for a light emitting device and a solar cell is characterized in that the hole transporting layer is formed by depositing nickel oxide (NiO) on a side of a conductive thin film formed of a flexible metal.
- NiO nickel oxide
- the conductive thin film may be formed of nickel or an alloy containing nickel.
- the nickel oxide may be formed by thermally treating the conductive thin film in oxygen atmosphere.
- the nickel oxide may be deposited using one of a physical vapor deposition process and a chemical vapor deposition process.
- a method of manufacturing a hole transporting layer for a light emitting device and a solar cell includes: preparing a conductive thin film formed of a flexible metal; and thermally treating the conductive thin film in oxygen atmosphere to form an oxide layer, thereby forming a hole transporting layer.
- a method of manufacturing a hole transporting layer for a light emitting device and a solar cell includes: preparing a conductive thin film formed of a flexible metal; and depositing an oxide layer on a surface of the conductive thin film in reaction gas atmosphere to form the hole transporting layer.
- the conductive thin film may be formed of nickel or an alloy containing nickel.
- the oxide layer may be formed of NiO.
- the forming of the oxide layer may be performed at about 50°C to about 1400°C.
- the nickel oxide may be deposited using one of a physical vapor deposition process and a chemical vapor deposition process.
- a content of oxygen contained in the reaction gas may increase or decrease.
- a substrate and an electrode that are essential component parts of the light emitting device or the solar cell are replaced with the flexible metal substrate, and a surface of the metal substrate is oxidized or deposited to form the hole transporting layer.
- the hole transporting layer that is more stable against oxygen or moisture of the atmosphere may be obtained.
- the oxygen content and heat treatment temperature of the reaction gas may be controlled to adjust characteristics required for the light emitting layer and the light absorbing layer.
- FIG. 1 is a schematic view of a light emitting device and a solar cell according to an embodiment.
- FIG. 2 is a flowchart illustrating a process of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- FIG. 3 is an image illustrating surface changes according to heat treatment temperature changes when a conductive thin film is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- FIG. 4 is a table illustrating resistivity and surface roughness changes according to heat treatment temperature changes when a conductive thin film is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- FIG. 5 is a table illustrating resistance and surface roughness changes according to oxygen content changes in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- FIG. 1 is a schematic view of a light emitting device and a solar cell according to an embodiment.
- a light emitting device has a configuration similar to that of a solar cell. That is, the light emitting device and the solar cell each includes an electrode, a conductive thin film 10, a hole transporting layer 20 disposed on a surface of the conductive thin film 10, an electron transporting layer disposed on a surface of the electrode, and a light emitting layer and a light absorbing layer, which are disposed between the electron transporting layer and the hole transporting layer 20.
- the light emitting layer is disposed between the electron transporting layer and the hole transporting layer 20.
- the light absorbing layer is disposed between the electron transporting layer and the hole transporting layer 20.
- the electrode, the electron transporting layer, the light emitting layer, and the light absorbing layer may be manufactured by a normal manufacturing process, their detailed description will be omitted.
- configurations of the conductive thin film 10 and the hole transporting layer 20 will be described in detail.
- the conductive thin film 10 serves as an electrode for supplying an electric charge and a support at the same time.
- the conductive thin film 10 may be formed of a metallic material having conductivity.
- the conductive thin film 10 is formed of an alloy containing nickel (Ni).
- the hole transporting layer 20 is disposed on the conductive thin film 10.
- the hole transporting layer 20 is a main part of this embodiment. A portion of the conductive thin film 10 is thermally treated, or a deposition process is performed on the conductive thin film 10 to form the hole transporting layer 20.
- the hole transporting layer 20 may correspond to an oxide layer formed by thermally treating an outer surface of the conductive thin film 10 in oxygen atmosphere or an oxide layer formed by performing a deposition process on an outer surface of the conductive thin film 10 in reaction gas atmosphere.
- the hole transporting layer 20 may be formed of nickel oxide (NiO) to contain Ni, like the conductive thin film 10.
- FIG. 2 is a flowchart illustrating a process of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- a method of manufacturing a hole transporting layer 20 includes a material preparation process (S100) for preparing a conductive thin film 10 formed of a flexible metal and an oxide layer formation process (S200) for forming an oxide layer corresponding to the hole transporting layer 20 at a side of the conductive thin film 10.
- S100 material preparation process
- S200 oxide layer formation process
- the conductive thin film 10 is formed of a conductive metal.
- the conductive thin film 10 may be formed of Ni or an alloy containing Ni.
- the oxide layer to be formed as the hole transporting layer 20 is formed.
- the oxide layer may be formed according to two embodiments.
- the conductive thin film 10 may be thermally treated at a temperature ranging from about 50°C to about 1400°C in oxygen atmosphere to form the oxide layer.
- a physical vapor deposition process or a chemical vapor deposition process may be performed on a surface of the conductive thin film 10 in reaction gas atmosphere to form the oxide layer.
- reaction gas contains oxygen, and thus, the composition of the oxide layer may be NiO.
- Conductive thin film Ni-5at.%W alloy metal tape, 4 mm(width) ⁇ 15 mm(length) ⁇ 0.8 mm(thickness)
- Atmosphere gas 100% oxygen, 2 L/min flow rate
- FIGS. 3 and 4 Experimental data with respect to a hole transporting layer 20 manufactured according to the first embodiment is shown in FIGS. 3 and 4.
- FIG. 3 is an image illustrating surface changes according to heat treatment temperature changes when a conductive thin film 10 is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- FIG. 4 is a table illustrating resistivity and surface roughness changes according to heat treatment temperature changes when a conductive thin film 10 is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- NiO to be used as a hole transporting layer 20 is formed on a surface of the conductive thin film 10.
- a surface roughness of NiO a surface roughness of Ni-5%W metal substrate was estimated as 7.723 nm in root-mean-square surface roughness (RMS).
- RMS root-mean-square surface roughness
- the surface roughness at about 500°C was estimated as 2.268 nm.
- the surface roughness is reduced while the heat treatment temperature increases from 0°C to 500°C because impurities such as an organism attached to a surface of the conductive thin film 10 are burned and removed. Also, as the heat treatment temperature gradually increases above 500°C, the surface roughness increased. As a result, the surface roughness at about 800°C was estimated as 70.221 nm.
- a surface color of the hole transporting layer 20 was exhibited as a metal color similar to that of a pure Ni-5at.%W substrate up to a temperature of about 400°C, a dark yellow at a temperature of about 500°C, and a green at a temperature greater than about 600°C.
- resistivity of the hole transporting layer was not significantly changed up to a heat treatment temperature of about 400°C.
- the heat treatment temperature is about 500°C
- the resistivity was measured between 10 -4 ⁇ cm and 10 -3 ⁇ cm
- the resistivity was measured between 10 -2 ⁇ cm and 10 2 ⁇ cm.
- the resistivity was in excess of 10 4 ⁇ cm.
- the heat treatment temperature may be more accurately controlled to obtain resistivity required for the hole transporting layer.
- Conductive thin film Ni-5at.%W alloy metal tape, 4 mm(width) ⁇ 15 mm(length) ⁇ 0.8 mm(thickness)
- Atmosphere gas Ar, O 2
- FIG. 5 is a table illustrating resistance and surface roughness changes according to oxygen content changes in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
- a sputtering deposition process is performed to form a hole transporting layer 20.
- a resistance of the hole transporting layer 20 was changed according to a change of oxygen content in an reaction gas mixed with oxygen and argon.
- the resistance of the hole transporting layer 20 was ⁇ 0.6 M ⁇ in pure argon gas atmosphere. However, as the oxygen content gradually increases to about 2.5%, about 5%, and about 10%, the resistance gradually decreased to about ⁇ 5 K ⁇ , about ⁇ 1 K ⁇ , and about ⁇ 100 ⁇ .
- the surface color of the hole transporting layer 20 was changed according to the change of oxygen content.
- the surface color was exhibited as a yellow in pure argon gas atmosphere. However, as the oxygen content increases, the surface color was gradually changed from a light blue to a dark blue, and finally, the surface color was exhibited as a violet.
- the surface roughness of the conductive thin film (Ni-5at.%W metal tape) on which the hole transporting layer 20 is not formed yet was about 5 nm.
- the surface roughness of the hole transporting layer 20 formed of NiO decreased to about 1 nm to about 2 nm.
- the conductive thin film has surface roughness greater than that of the conductive thin film (Ni-5at.%W metal tape) on which the hole transporting layer 20 is not formed yet. This is done because a large amount of oxygen gas is supplied during the sputtering deposition process to cause grain growth of NiO.
- the conductive thin film is formed of a nickel alloy in the embodiments, the present disclosure is not limited thereto.
- the conductive thin film may be formed of pure nickel if the oxide layer (NiO) can be formed by thermally treating the conductive thin film in the oxide layer formation process.
- the conductive thin film is formed of a metal containing nickel in the embodiments, the present disclosure is not limited thereto.
- the conductive thin film may be formed of conductive metals if the oxide layer (NiO) can be formed by the deposition in the oxide layer formation process.
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Abstract
Provided are a hole transporting layer for a light emitting device and a solar cell and a method for manufacturing the same. The hole transporting layer for the light emitting device and the solar cell is formed of nickel oxide (NiO) formed by oxidizing a side of a conductive thin film formed of a flexible metal. A method of manufacturing a hole transporting layer for a light emitting device and a solar cell includes preparing a conductive thin film formed of a flexible metal and thermally treating the conductive thin film in oxygen atmosphere to form an oxide layer, thereby forming a hole transporting layer. Therefore, productivity can be improved, and the hole transporting layer adapted for the light emitting device and the solar cell can be manufactured by selectively changing formation conditions when the oxide layer is formed.
Description
The present disclosure relates to a hole transporting layer for light emitting devices and solar cells and a method for manufacturing the same.
Today, light emitting devices using semiconductor nanocrystals or puantum-dots have advantages of self-luminescence and low power consumption, as well as can realize color reproduction of high purity, high brightness, and high efficiency by quantum confinement effects due to the semiconductor nanocrystals with particle size of about several nanometers. Thus, the light emitting devices using semiconductor nanocrystals are considered as the next-generation electro-optical device.
Such a light emitting device has a structure similar to that of a solar cell. The light emitting device includes a substrate, a transparent electrode, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electrode. The solar cell includes a substrate, a transparent electrode, a hole transporting layer, a light absorbing layer, an electron transporting layer, and an electrode.
The transparent electrode of the light emitting device and solar cell serves as an electrode and transmits light.
Thus, an indium tin oxide (ITO) film is widely used as the transparent electrode.
However, to use the ITO film as the transparent electrode, the ITO film should have a thick thickness to realize low resistivity. On the other hand, as the ITO film gets thicker, light transmittance thereof is low. Thus, there is a limitation that the ITO film is used as the conductive thin film of the light emitting device.
In addition, since indium (In) used as a raw material of the ITO film is a rare metal having limited reserves, the light emitting device and the solar cell gradually increase in price.
The hole transporting layer is necessary for effectively transporting holes to the light emitting layer. Also, the hole transporting layer having proper hole concentration and electrical conductivity according to characteristics of the light emitting layer is required. Thus, the hole transporting layer should have a thin thickness in order to have proper hole concentration and electrical conductivity and transmit a large amount of light.
However, there is a limit to adjust hole concentration, electrical conductivity, and light transmittance through only a thickness of the hole transporting layer. As a result, other materials suited for characteristics of respective light emitting layers should be used, and thus, the hole transporting layer is limited in material.
Embodiments provide a hole transporting layer for light emitting devices and solar cells, in which a substrate and an electrode that are essential component parts of the light emitting device or the solar cell are replaced with a flexible metal substrate, and a surface of the metal substrate is oxidized or deposited to form the hole transporting layer and a method for manufacturing the same.
In one embodiment, a hole transporting layer for a light emitting device and a solar cell is characterized in that the hole transporting layer is formed of nickel oxide (NiO) formed by oxidizing a side of a conductive thin film formed of a flexible metal.
In another embodiment, a hole transporting layer for a light emitting device and a solar cell is characterized in that the hole transporting layer is formed by depositing nickel oxide (NiO) on a side of a conductive thin film formed of a flexible metal.
The conductive thin film may be formed of nickel or an alloy containing nickel.
The nickel oxide may be formed by thermally treating the conductive thin film in oxygen atmosphere.
The nickel oxide may be deposited using one of a physical vapor deposition process and a chemical vapor deposition process.
In further another embodiment, a method of manufacturing a hole transporting layer for a light emitting device and a solar cell includes: preparing a conductive thin film formed of a flexible metal; and thermally treating the conductive thin film in oxygen atmosphere to form an oxide layer, thereby forming a hole transporting layer.
In even further another embodiment, a method of manufacturing a hole transporting layer for a light emitting device and a solar cell includes: preparing a conductive thin film formed of a flexible metal; and depositing an oxide layer on a surface of the conductive thin film in reaction gas atmosphere to form the hole transporting layer.
In the preparing of the conductive thin film, the conductive thin film may be formed of nickel or an alloy containing nickel.
In the forming of the oxide layer, the oxide layer may be formed of NiO.
The forming of the oxide layer may be performed at about 50℃ to about 1400℃.
In the forming of the oxide layer, the nickel oxide may be deposited using one of a physical vapor deposition process and a chemical vapor deposition process.
In the forming of the oxide layer, a content of oxygen contained in the reaction gas may increase or decrease.
According to the embodiments, a substrate and an electrode that are essential component parts of the light emitting device or the solar cell are replaced with the flexible metal substrate, and a surface of the metal substrate is oxidized or deposited to form the hole transporting layer.
Thus, a multi-layered structure of the light emitting device and the solar cell may be simplified.
Also, the hole transporting layer that is more stable against oxygen or moisture of the atmosphere may be obtained.
In addition, the oxygen content and heat treatment temperature of the reaction gas may be controlled to adjust characteristics required for the light emitting layer and the light absorbing layer.
FIG. 1 is a schematic view of a light emitting device and a solar cell according to an embodiment.
FIG. 2 is a flowchart illustrating a process of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
FIG. 3 is an image illustrating surface changes according to heat treatment temperature changes when a conductive thin film is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
FIG. 4 is a table illustrating resistivity and surface roughness changes according to heat treatment temperature changes when a conductive thin film is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
FIG. 5 is a table illustrating resistance and surface roughness changes according to oxygen content changes in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
Hereinafter, configurations of a light emitting device and a solar cell according to an embodiment will be described with reference to FIG. 1.
FIG. 1 is a schematic view of a light emitting device and a solar cell according to an embodiment.
Referring to FIG. 1, a light emitting device has a configuration similar to that of a solar cell. That is, the light emitting device and the solar cell each includes an electrode, a conductive thin film 10, a hole transporting layer 20 disposed on a surface of the conductive thin film 10, an electron transporting layer disposed on a surface of the electrode, and a light emitting layer and a light absorbing layer, which are disposed between the electron transporting layer and the hole transporting layer 20.
That is, in case of the light emitting device, the light emitting layer is disposed between the electron transporting layer and the hole transporting layer 20. In case of the solar cell, the light absorbing layer is disposed between the electron transporting layer and the hole transporting layer 20.
Since the electrode, the electron transporting layer, the light emitting layer, and the light absorbing layer may be manufactured by a normal manufacturing process, their detailed description will be omitted. Hereinafter, configurations of the conductive thin film 10 and the hole transporting layer 20 will be described in detail.
The conductive thin film 10 serves as an electrode for supplying an electric charge and a support at the same time. The conductive thin film 10 may be formed of a metallic material having conductivity. In this embodiment, the conductive thin film 10 is formed of an alloy containing nickel (Ni).
The hole transporting layer 20 is disposed on the conductive thin film 10. The hole transporting layer 20 is a main part of this embodiment. A portion of the conductive thin film 10 is thermally treated, or a deposition process is performed on the conductive thin film 10 to form the hole transporting layer 20.
That is, the hole transporting layer 20 may correspond to an oxide layer formed by thermally treating an outer surface of the conductive thin film 10 in oxygen atmosphere or an oxide layer formed by performing a deposition process on an outer surface of the conductive thin film 10 in reaction gas atmosphere.
Thus, the hole transporting layer 20 may be formed of nickel oxide (NiO) to contain Ni, like the conductive thin film 10.
Hereinafter, a method of manufacturing a hole transporting layer 20 will be described with reference to FIG. 2.
FIG. 2 is a flowchart illustrating a process of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
Referring to FIG. 2, a method of manufacturing a hole transporting layer 20 includes a material preparation process (S100) for preparing a conductive thin film 10 formed of a flexible metal and an oxide layer formation process (S200) for forming an oxide layer corresponding to the hole transporting layer 20 at a side of the conductive thin film 10.
In the material preparation process (S100), the conductive thin film 10 is formed of a conductive metal. For example, the conductive thin film 10 may be formed of Ni or an alloy containing Ni.
Thereafter, in the oxide layer formation process (S200), the oxide layer to be formed as the hole transporting layer 20 is formed. At this time, in the oxide layer formation process (200), the oxide layer may be formed according to two embodiments.
That is, in an embodiment, the conductive thin film 10 may be thermally treated at a temperature ranging from about 50℃ to about 1400℃ in oxygen atmosphere to form the oxide layer. In another embodiment, a physical vapor deposition process or a chemical vapor deposition process may be performed on a surface of the conductive thin film 10 in reaction gas atmosphere to form the oxide layer.
Here, the reaction gas contains oxygen, and thus, the composition of the oxide layer may be NiO.
Hereinafter, the embodiments will be described.
[first embodiment]
Conductive thin film: Ni-5at.%W alloy metal tape, 4 mm(width)×15 mm(length)×0.8 mm(thickness)
Heat treatment temperature: 0 - 800℃
Atmosphere gas: 100% oxygen, 2 L/min flow rate
Experimental data with respect to a hole transporting layer 20 manufactured according to the first embodiment is shown in FIGS. 3 and 4.
That is, FIG. 3 is an image illustrating surface changes according to heat treatment temperature changes when a conductive thin film 10 is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment. FIG. 4 is a table illustrating resistivity and surface roughness changes according to heat treatment temperature changes when a conductive thin film 10 is thermally treated in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment.
As shown in FIGS. 3 and 4, when a conductive thin film 10 containing Ni-5at.%W alloy is thermally treated, NiO to be used as a hole transporting layer 20 is formed on a surface of the conductive thin film 10. In a surface roughness of NiO, a surface roughness of Ni-5%W metal substrate was estimated as 7.723 nm in root-mean-square surface roughness (RMS). Also, as the heat treatment temperature gradually increases, the surface roughness gradually decreased. As a result, the surface roughness at about 500℃ was estimated as 2.268 nm.
According to the results, it may be determined that the surface roughness is reduced while the heat treatment temperature increases from 0℃ to 500℃ because impurities such as an organism attached to a surface of the conductive thin film 10 are burned and removed. Also, as the heat treatment temperature gradually increases above 500℃, the surface roughness increased. As a result, the surface roughness at about 800℃ was estimated as 70.221 nm.
A surface color of the hole transporting layer 20 was exhibited as a metal color similar to that of a pure Ni-5at.%W substrate up to a temperature of about 400℃, a dark yellow at a temperature of about 500℃, and a green at a temperature greater than about 600℃.
Thus, since surface roughness is very important in the semiconductor nanocrystals, i.e., the light emitting device and the solar cell using quantum-dot, a physical or chemical polishing process was performed on the hole transporting layer (NiO) to obtain a surface roughness value of less than about 2 nm.
At this time, resistivity of the hole transporting layer was not significantly changed up to a heat treatment temperature of about 400℃. However, when the heat treatment temperature is about 500℃, the resistivity was measured between 10-4 Ωㆍcm and 10-3 Ωㆍcm, and when the heat treatment temperature is about 600℃, the resistivity was measured between 10-2 Ωㆍcm and 102 Ωㆍcm. Also, when the heat treatment temperature increases over about 700℃, the resistivity was in excess of 104 Ωㆍcm.
Thus, when viewing the results, during the formation of the hole transporting layer through the heat treatment process, the heat treatment temperature may be more accurately controlled to obtain resistivity required for the hole transporting layer.
[second embodiment]
Conductive thin film: Ni-5at.%W alloy metal tape, 4 mm(width)×15 mm(length)×0.8 mm(thickness)
Base vacuum: 〈5×10-6 Torr
Atmosphere gas: Ar, O2
Deposition temperature: room temperature
Deposition pressure: ~6m Torr
Deposition time: 20 minutes
Experimental data with respect to a hole transporting layer manufactured according to the second embodiment is shown in FIG. 5.
That is, FIG. 5 is a table illustrating resistance and surface roughness changes according to oxygen content changes in an oxide layer formation process that is one process of processes of manufacturing a hole transporting layer for a light emitting device and a solar cell according to an embodiment. In the oxide layer formation process (S200), a sputtering deposition process is performed to form a hole transporting layer 20.
As shown in FIG. 5, a resistance of the hole transporting layer 20 was changed according to a change of oxygen content in an reaction gas mixed with oxygen and argon.
That is, the resistance of the hole transporting layer 20 was ~0.6 MΩ in pure argon gas atmosphere. However, as the oxygen content gradually increases to about 2.5%, about 5%, and about 10%, the resistance gradually decreased to about ~5 KΩ, about ~1 KΩ, and about ~100 Ω.
Also, the surface color of the hole transporting layer 20 was changed according to the change of oxygen content.
That is, the surface color was exhibited as a yellow in pure argon gas atmosphere. However, as the oxygen content increases, the surface color was gradually changed from a light blue to a dark blue, and finally, the surface color was exhibited as a violet.
The surface roughness of the conductive thin film (Ni-5at.%W metal tape) on which the hole transporting layer 20 is not formed yet was about 5 nm. On the other hand, the surface roughness of the hole transporting layer 20 formed of NiO decreased to about 1 nm to about 2 nm.
In case where the reaction gas containing about 10% oxygen is injected, the conductive thin film has surface roughness greater than that of the conductive thin film (Ni-5at.%W metal tape) on which the hole transporting layer 20 is not formed yet. This is done because a large amount of oxygen gas is supplied during the sputtering deposition process to cause grain growth of NiO.
The invention may should not be construed as being limited to the embodiments, and be embodied in many different forms based on the invention by those of ordinary skill in the art without departing from the spirit and scope of the invention.
For example, although the conductive thin film is formed of a nickel alloy in the embodiments, the present disclosure is not limited thereto. For example, it is obvious that the conductive thin film may be formed of pure nickel if the oxide layer (NiO) can be formed by thermally treating the conductive thin film in the oxide layer formation process.
Also, although the conductive thin film is formed of a metal containing nickel in the embodiments, the present disclosure is not limited thereto. For example, the conductive thin film may be formed of conductive metals if the oxide layer (NiO) can be formed by the deposition in the oxide layer formation process.
Claims (12)
- A hole transporting layer for a light emitting device and a solar cell, characterized in that the hole transporting layer is formed of nickel oxide (NiO) formed by oxidizing a side of a conductive thin film formed of a flexible metal.
- A hole transporting layer for a light emitting device and a solar cell, characterized in that the hole transporting layer is formed by depositing nickel oxide (NiO) on a side of a conductive thin film formed of a flexible metal.
- The hole transporting layer according to claim 1 or 2, wherein the conductive thin film is formed of nickel or an alloy containing nickel.
- The hole transporting layer according to claim 1, wherein the nickel oxide is formed by thermally treating the conductive thin film in oxygen atmosphere.
- The hole transporting layer according to claim 2, wherein the nickel oxide is deposited using one of a physical vapor deposition process and a chemical vapor deposition process.
- A method of manufacturing a hole transporting layer for a light emitting device and a solar cell, the method comprising:preparing a conductive thin film formed of a flexible metal; andthermally treating the conductive thin film in oxygen atmosphere to form an oxide layer, thereby forming a hole transporting layer.
- A method of manufacturing a hole transporting layer for a light emitting device and a solar cell, the method comprising:preparing a conductive thin film formed of a flexible metal; anddepositing an oxide layer on a surface of the conductive thin film in reaction gas atmosphere to form the hole transporting layer.
- The method according to claim 6 or 7, wherein, in the preparing of the conductive thin film, the conductive thin film is formed of nickel or an alloy containing nickel.
- The method according to claim 8, wherein, in the forming of the oxide layer, the oxide layer is formed of NiO.
- The method according to claim 6, wherein the forming of the oxide layer is performed at about 50℃ to about 1400℃.
- The method according to claim 7, wherein, in the forming of the oxide layer, the nickel oxide is deposited using one of a physical vapor deposition process and a chemical vapor deposition process.
- The method according to claim 11, wherein, in the forming of the oxide layer, a content of oxygen contained in the reaction gas increases or decreases.
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KR1020090064705A KR101104675B1 (en) | 2009-07-16 | 2009-07-16 | A Hole transporting layer for Light emitting devices and method for manufacturing thereof |
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JP2005190998A (en) * | 2003-12-02 | 2005-07-14 | Semiconductor Energy Lab Co Ltd | Light-emitting element and light-emitting device using same |
KR20060003920A (en) * | 2004-07-05 | 2006-01-12 | 오창석 | Gan based light emitting device using ni metal as a p-contact current spreading layer |
KR20080035745A (en) * | 2006-10-20 | 2008-04-24 | 주식회사 와이텔포토닉스 | Optical device package and method for manufacturing thereof |
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JP2005190998A (en) * | 2003-12-02 | 2005-07-14 | Semiconductor Energy Lab Co Ltd | Light-emitting element and light-emitting device using same |
KR20060003920A (en) * | 2004-07-05 | 2006-01-12 | 오창석 | Gan based light emitting device using ni metal as a p-contact current spreading layer |
KR20080035745A (en) * | 2006-10-20 | 2008-04-24 | 주식회사 와이텔포토닉스 | Optical device package and method for manufacturing thereof |
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WO2023168627A1 (en) * | 2022-03-09 | 2023-09-14 | 宁德时代新能源科技股份有限公司 | Perovskite solar cell and preparation method therefor |
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