CN115394929A - Quantum dot device and preparation method thereof - Google Patents
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
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Abstract
The application relates to the technical field of illumination, and provides a quantum dot device and a preparation method thereof. The quantum dot device comprises an anode and a cathode which are oppositely arranged, a blue light quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transmission layer arranged between the cathode and the blue light quantum dot light-emitting layer; wherein the electron transport material constituting the electron transport layer comprises: red light quantum dot material, green light quantum dot material and inorganic electron transport material. According to the quantum dot device, the electron transmission layer can play a role in electron transmission and also serves as a light conversion layer to convert the light emission of the blue light quantum dots into red light and green light, so that the effect of emitting white light by the device is achieved.
Description
Technical Field
The application belongs to the technical field of lighting, and particularly relates to a quantum dot device and a preparation method thereof.
Background
The quantum dots have the advantages of tunable light-emitting wavelength, narrow light-emitting line width, high light-emitting efficiency, good light, heat and chemical stability and the like, can be integrated into an electroluminescent device after film formation to serve as an effective exciton radiation recombination center, and can be applied to solid-state illumination and full-color flat panel display to become a new-generation luminescent material. Compared with the traditional fluorescent powder LED and the current OLED, the LED based on the quantum dots has the advantages of wide color gamut, high color purity, low power consumption, low cost, easiness in processing and the like when being used for displaying and illuminating.
Although the QLED is an ideal healthy eye-protecting light source as a semiconductor lighting technology with soft light emitting, the QLED has attractive application prospect in the field of lighting. However, only OLED lighting products are still on the market today. The OLED lighting product has a complex structure, the synthesis of key materials is complex, the synthesis yield of high-purity materials is low, and the utilization rate of the materials in the evaporation process is low. Therefore, it is important to develop a white light illumination device based on quantum dot material.
Disclosure of Invention
The application aims to provide a quantum dot device and a preparation method thereof, and aims to solve the problem that no QLED device capable of emitting white light exists in the market.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
the application provides a quantum dot device in a first aspect, which comprises an anode and a cathode which are oppositely arranged, a blue light quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transmission layer arranged between the cathode and the blue light quantum dot light-emitting layer; wherein the electron transport material constituting the electron transport layer includes: red light quantum dot material, green light quantum dot material and inorganic electron transport material.
The second aspect of the present application provides a method for manufacturing a quantum dot device, comprising the following steps:
preparing a hole injection layer on an anode substrate, preparing a hole transport layer on the surface of one side of the hole injection layer, which is far away from the anode substrate, and preparing a blue light quantum dot light emitting layer on the surface of one side of the hole transport layer, which is far away from the hole injection layer;
preparing an electron transport layer on the surface of one side, away from the hole transport layer, of the blue light quantum dot light-emitting layer, wherein the electron transport material for forming the electron transport layer comprises: red light quantum dot material, green light quantum dot material and inorganic electron transmission material;
and preparing a cathode on the surface of one side of the electron transmission layer, which is far away from the blue light quantum dot light-emitting layer.
According to the quantum dot device, the red light quantum dot material and the green light quantum dot material are doped in the inorganic electron transport material and serve as the electron transport layer material. The obtained electron transmission layer can play a role of electron transmission, and can also be used as a light conversion layer to convert the luminescence of the blue light quantum dots into red light and green light, thereby realizing the effect of white light emission of the device. Specifically, the red light quantum dot material and the green light quantum dot material respectively emit red light and green light under the excitation of blue light emitted by the blue light quantum dot. The red light and the green light are combined with the blue light emitted by the blue light quantum dots to form white light. Compared with a white light OLED lighting device, the quantum dot device provided by the application has the advantages of simple structure, easily obtained materials, high material quality and capability of improving the processability of the device.
According to the preparation method of the quantum dot device, the hole injection layer, the hole transport layer, the quantum dot light emitting layer, the electron transport layer and the cathode are sequentially prepared on the anode substrate.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
Fig. 1 is a schematic structural diagram of a quantum dot device provided in an embodiment of the present application;
fig. 2 is a flow chart of a manufacturing process of a quantum dot device according to an embodiment of the present disclosure.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The term "LED" is an abbreviation for "light-emitting diode", representing a light-emitting diode;
the term "QLED" is an abbreviation for "Quantum Dot Light Emitting Diodes," which means a Quantum Dot Light Emitting diode;
the term "OLED" is an abbreviation of "organic light-Emitting Diode"), also known as organic electroluminescent display, organic light-Emitting Diode.
The simplest QLED device consists of a cathode, an electron transport layer, a quantum dot layer, a hole transport layer, and an anode. In the QLED device, a quantum dot film is clamped in the middle of a charge transport layer, when forward bias is applied to two ends of the QLED device, electrons and holes enter a quantum dot light-emitting layer through the electron transport layer and a hole transport layer respectively, and the electrons and the holes are recombined in quantum dots to emit light. And when the quantum dots are hit by light, they can emit light of their own color. The quantum dots excited by light cooperate with the light emitting diode of quantum dots to produce composite light, such as white light. In view of this, it is preferable that,
as shown in fig. 1, a first aspect of the embodiments of the present application provides a quantum dot device, which includes an anode 1 and a cathode 6 that are oppositely disposed, a blue quantum dot light emitting layer 4 disposed between the anode 1 and the cathode 6, and an electron transport layer 5 disposed between the cathode 6 and the blue quantum dot light emitting layer 4; wherein the electron transport material constituting the electron transport layer 5 includes: red light quantum dot material, green light quantum dot material and inorganic electron transport material.
According to the quantum dot device provided by the embodiment of the application, the red light quantum dot material and the green light quantum dot material are doped in the inorganic electron transport material and serve as the electron transport layer material. The electron transport layer 5 thus obtained can not only play a role of electron transport, but also serve as a light conversion layer to convert the luminescence of the blue light quantum dots into red light and green light, thereby realizing the effect of white light emission of the device. Specifically, the red light quantum dot material and the green light quantum dot material respectively emit red light and green light under the excitation of blue light emitted by the blue light quantum dot. The red light and the green light are compounded with the blue light emitted by the blue light quantum dots, and white light can be formed. Compared with a white light OLED lighting device, the quantum dot device provided by the application has the advantages that the device structure is simple, the materials are easy to obtain, the material quality is high, and the processability of the device is improved.
In the embodiment of the present application, the inorganic electron transport material in the electron transport material, on the one hand, serves as the functional material of the electron transport layer 5 to exert the electron transport effect, and on the other hand, the inorganic electron transport material has the light scattering property, and as the light scattering particles of the red light quantum dot material and the green light quantum dot material, the inorganic electron transport material can exert the light scattering effect without additionally adding the light scattering particles, thereby increasing the light conversion efficiency.
In some embodiments, the inorganic electron transport material is a nano-metal oxide. The nanometer metal oxide can be used as light scattering particles of red light quantum dot materials and green light quantum dot materials, plays a role in light scattering, and improves light conversion efficiency. In some embodiments, the nano-metal oxide comprises ZnO, zn x Mg y O、Zn x Al y O、Zn x Mg y Li z At least one of O. The nanometer metal oxides have good light scattering effect, and are beneficial to realizing the excitation of blue light on red light quantum dot materials and green light quantum dot materials in the electron transmission layer.
In embodiments of the present application, the red light quantum dot material is selected from quantum dots capable of emitting red light, and in some embodiments, the red light quantum dot material is selected from CdSe, cdS, cuInS 2 、AgInS 2 InP, but not limited thereto. The green quantum dot material is selected from quantum dots capable of emitting green light, and in some embodiments, the green quantum dot material is selected from CdSe, cdS, cuInS 2 、AgInS 2 InP, but not limited thereto.
In some embodiments, the weight percentage of the red light quantum dot material is 5% to 30% and the weight percentage of the green light quantum dot material is 5% to 30% based on 100% of the total weight of the electron transport material. Under the condition, the red light quantum dot material and the green light quantum dot material have proper content, can respectively generate red light and green light after being excited by blue light, ensure the proper intensity of the red light and the green light, and can form white light after being compounded with the blue light.
In some embodiments, the sum of the weight percentages of the red and green quantum dot materials is 5% to 50% based on 100% of the total weight of the electron transport material. In this case, the content of the inorganic electron transport material in the electron transport material is 50% to 95%, so that a certain electron transport property can be ensured.
The thickness of the electron transport layer 5 affects two aspects, namely the light conversion efficiency, i.e. the efficiency of conversion of blue light into red and green light. The thicker the electron transport layer 5 is, the higher the conversion efficiency is, and since the quantum dot white light emitting diode needs to be obtained in the embodiment of the present application, the blue light cannot be completely converted into red light and green light, and only can be partially converted. And secondly, the electron transmission capability is reduced along with the increase of the thickness. In order to take both the light conversion efficiency and the electron transmission capability into consideration, in some embodiments, the thickness of the electron transmission layer 5 is 0.05 to 5um, and under such a condition, the red light quantum dot material and the green light quantum dot material in the electron transmission layer 5 can be endowed with good light conversion efficiency, so as to emit light under the excitation of blue light, and further, the blue light generated by the blue light quantum dot light emitting diode is compounded with the red light and the green light respectively generated by the red light quantum dot material and the green light quantum dot material under the excitation of blue light to form white light.
Because electron transport layer 5 has certain thickness, just can realize better light conversion efficiency, be about to partly blue light transform into ruddiness and green glow behind the electron transport layer, but thicker electron transport layer 5 sets up when the light-emitting side, can influence the luminousness of quantum dot device. Thus, in some embodiments, the quantum dot white light device is an inverted quantum dot device. In this case, in the top emission device, the electron transport layer 5 may adopt a weak microcavity structure, and a certain thickness is set, so that not only can the conversion efficiency of blue light be ensured, but also a basic electron transport function can be provided.
In some embodiments, the quantum dot device further comprises: a hole transport layer 3 disposed between the anode 1 and the blue quantum dot light emitting layer 4, and a hole injection layer 2 disposed between the hole transport layer 3 and the anode 1.
In some embodiments, the quantum dot device further comprises an electron injection layer (not shown) disposed between the cathode 6 and the electron transport layer 5.
In some embodiments, the material of the anode 1 may be one or more of Indium Tin Oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum doped zinc oxide (AZO), metal material. In some embodiments, the anode 1 is a composite anode formed of ITO/Ag/ITO (one Ag layer disposed in two ITO films). In some embodiments, the thickness of the anode 1 is greater than 80nm.
The material of the hole injection layer 2 is a hole injection material, and in some embodiments, the hole injection material is selected from a conductive polymer material such as polythiophene and polyaniline, and a derivative thereof. In some embodiments, the hole injection layer 2 has a thickness of 10-40nm.
The material of the hole transport layer 2 is a hole transport material, and in some embodiments, the hole transport material is selected from TFB, poly [ bis (4-phenyl) (4-butylphenyl) amine ] (Poly-TPD), polyvinylcarbazole (PVK), but is not limited thereto. In some embodiments, the thickness of the hole transport layer 2 is 5 to 50nm.
The blue light quantum dot light-emitting layer 4 is made of a blue light quantum dot material capable of emitting blue light, and in some embodiments, the blue light quantum dot material is selected from ZnSe blue light quantum dots or a blue light quantum dot material taking CdZnSe as a core. In some embodiments, the thickness of the blue quantum dot light emitting layer 4 is 6-30nm.
The electron injection layer may be made of a conventional material for electron injection.
The cathode 6 is a transparent electrode, and the cathode material may be one or more of transparent ITO, IZO, AZO, and IGZO. In some embodiments, the thickness of cathode 6 is 0.1-5um.
The quantum dot device provided by the embodiment of the application can be prepared by the following method.
As shown in fig. 2, a second aspect of the embodiments of the present application provides a method for manufacturing a quantum dot device, including the following steps:
s01, preparing a hole injection layer on an anode substrate, preparing a hole transport layer on the surface of one side, away from the anode substrate, of the hole injection layer, and preparing a blue light quantum dot light emitting layer on the surface of one side, away from the hole injection layer, of the hole transport layer;
s02, preparing an electron transport layer on the surface of one side, away from the hole transport layer, of the blue light quantum dot light-emitting layer, wherein the electron transport material for forming the electron transport layer comprises: red light quantum dot material, green light quantum dot material and inorganic electron transmission material;
and S03, preparing a cathode on the surface of one side, away from the blue light quantum dot light emitting layer, of the electron transmission layer.
According to the preparation method of the quantum dot device, the hole injection layer, the hole transport layer, the quantum dot light emitting layer, the electron transport layer and the cathode are sequentially prepared on the anode substrate.
In the embodiment of the present application, the material selection and the thickness setting of each layer are as described above, and are not repeated herein for brevity.
Specifically, in step S01, the anode substrate is prepared by the following method: preparing an ITO layer, a silver layer and an ITO layer on one side of the substrate to obtain the ITO/Ag/ITO substrate.
In some embodiments, the preparation of the hole injection layer on the anode substrate, the preparation of the hole transport layer on the surface of the hole injection layer, which is away from the anode substrate, and the preparation of the blue light quantum dot light emitting layer on the surface of the hole transport layer, which is away from the hole injection layer, can be realized by a solution processing method, so that the processability of the quantum dot white light device is improved.
In the step S02, an electron transport material containing a red light quantum dot material, a green light quantum dot material and an inorganic electron transport material is formed on the surface of one side of the blue light quantum dot light-emitting layer away from the hole transport layer, so as to obtain the electron transport layer.
In some embodiments, preparing an electron transport layer on a side surface of the blue quantum dot light emitting layer facing away from the hole transport layer comprises:
s031, prepare the electron transport material solution including red light quantum dot material, green light quantum dot material and inorganic electron transport material.
The types and relative contents of the red light quantum dot material, the green light quantum dot material and the inorganic electron transport material in the step are as described above, and are not described herein again for the sake of brevity. In yet another embodiment, a light quantum dot material, a green light quantum dot material, and an inorganic electron transport material are dispersed in a solvent to obtain an electron transport material solution.
S032, depositing an electron transport material solution on the surface of one side, away from the hole transport layer, of the blue light quantum dot light-emitting layer.
In the step, an electron transport material solution is deposited on the surface of one side, away from the hole transport layer, of the blue light quantum dot light-emitting layer through a solution processing method, so that the flatness of the film layer is improved, and the processability of the quantum dot white light device is improved through a solution processing method for matching other functional layers.
And S033, annealing to obtain the electronic transmission layer.
The residual solvent is removed through annealing treatment, and the electron transport material is dried to form a film. In some embodiments, the annealing temperature is 80 ℃ to 170 ℃ for 5min to 60min. By increasing the temperature of the annealing treatment, the electron transport properties of the electron transport layer are improved.
In some embodiments, the electron transport layer has a thickness of 0.05 to 5um. In the step S03, a cathode is prepared on the surface of the electron transport layer facing away from the blue light quantum dot light emitting layer, so as to obtain the quantum dot white light device. In some embodiments, a cathode is sputtered on the surface of the electron transport layer on the side facing away from the blue quantum dot light emitting layer.
In the embodiment of the present application, the solution processing method includes, but is not limited to, coating, doctor-blading, spin-coating, drop-coating, inkjet printing, and the like, and the dry film layer can be obtained by forming a film by the solution processing method and then drying the solvent.
The following description will be given with reference to specific examples.
Example 1
A quantum dot white light device comprises an anode and a cathode which are oppositely arranged, a blue light quantum dot light-emitting layer arranged between the anode and the cathode, a hole transport layer arranged between the anode and the blue light quantum dot light-emitting layer, a hole injection layer arranged between the hole transport layer and the blue light quantum dot light-emitting layer, and an electron transport layer arranged between the cathode and the blue light quantum dot light-emitting layer; wherein the electron transport material constituting the electron transport layer comprises: red light quantum dot material, green light quantum dot material and inorganic electron transport material. The anode is an ITO/Ag/ITO anode, the hole injection layer is poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT: PSS), the hole transport layer is poly [ (9, 9-dioctyl fluorenyl-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butyl phenyl) diphenylamine) ] (TFB), the blue light quantum dot light emitting layer is ZnSe/ZnS, the red light quantum dot is CdZnSe/ZnSe/ZnS, the green light quantum dot is CdZnSe/CdZnSe/ZnS, the inorganic electron transport material is ZnO, and the cathode is an ITO quantum dot white light device, wherein the preparation method comprises the following steps:
coating a hole injection material solution on the anode substrate to prepare a hole injection layer; coating a hole transport material solution on the surface of one side of the hole injection layer, which is far away from the anode substrate, so as to prepare a hole transport layer; coating a blue light quantum dot solution on the surface of one side of the hole transport layer, which is far away from the hole injection layer, to prepare a blue light quantum dot light-emitting layer;
coating a mixed solution of a red light quantum dot material, a green light quantum dot material and an inorganic electron transport material on one side of the blue light quantum dot light-emitting layer, which is far away from the hole transport layer, and annealing for 15min at the temperature of 120 ℃ to prepare an electron transport layer with the thickness of 0.5 um; wherein, the red light quantum dot material accounts for 15 percent of the total weight of the electron transport material, and the green light quantum dot material accounts for 25 percent of the total weight of the electron transport material.
And evaporating a cathode on the surface of one side of the electron transmission layer, which deviates from the blue light quantum dot light-emitting layer, so as to obtain the quantum dot white light device.
Example 2
A quantum dot white light device, different from embodiment 1 in that: the proportion of the red light quantum dot material and the green light quantum dot material in the total weight of the electron transport material is different. Specifically, the red light quantum dot material accounts for 10% of the total weight of the electron transport material, and the green light quantum dot material accounts for 30% of the total weight of the electron transport material.
Example 3
A quantum dot white light device, which is different from embodiment 1 in that: the thickness of the electron transport layer and the proportion of the red and green quantum dot materials in the total weight of the electron transport material are different. Specifically, the red light quantum dot material accounts for 5% of the total weight of the electron transport material, the green light quantum dot material accounts for 15% of the total weight of the electron transport material, and the thickness of the electron transport layer is 1um.
The quantum dot white light devices provided in examples 1 to 3 were subjected to performance tests, and color coordinate scores were measured as (0.45, 0.32), (0.32, 0.37), (0.33, 0.36), and it was found that quantum dot white light devices can be obtained by the method provided in the examples of the present application.
The present invention is not intended to be limited to the particular embodiments shown and described, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed.
Claims (12)
1. A quantum dot device is characterized by comprising an anode and a cathode which are oppositely arranged, a blue light quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transmission layer arranged between the cathode and the blue light quantum dot light-emitting layer; wherein the electron transport material constituting the electron transport layer includes: red light quantum dot material, green light quantum dot material and inorganic electron transport material.
2. The quantum dot device of claim 1, wherein the red quantum dot material is 5-30 wt% and the green quantum dot material is 5-30 wt% based on 100 wt% of the total weight of the electron transport material.
3. The quantum dot device of claim 2, wherein the sum of the weight percentages of the red and green quantum dot materials is 5% to 50% based on the total weight of the electron transport material taken as 100%.
4. The quantum dot device of claim 1, wherein the electron transport layer has a thickness of 0.05 to 5um.
5. The quantum dot device of any of claims 1 to 4, wherein the electron transport layer acts as a light conversion layer to convert light emitted by the blue quantum dot layer into red and green light, resulting in a device emitting white light.
6. The quantum dot device of any of claims 1 to 4, wherein the inorganic electron transport material is a nano metal oxide.
7. The quantum dot device of claim 6, wherein the nano-metal oxide comprises ZnO, zn x Mg y O、Zn x Al y O、Zn x Mg y Li z At least one of O.
8. The quantum dot white light device according to any one of claims 1 to 4, wherein the quantum dot white light device is an inverted quantum dot white light device.
9. The quantum dot device of any one of claims 1 to 4, wherein the quantum dot white light device further comprises a hole transport layer disposed between the anode and the blue quantum dot light emitting layer and a hole injection layer disposed between the hole transport layer and the anode; and/or
The quantum dot device further includes an electron injection layer disposed between the cathode and the electron transport layer.
10. A preparation method of a quantum dot device is characterized by comprising the following steps:
preparing a hole injection layer on an anode substrate, preparing a hole transport layer on the surface of one side, away from the anode substrate, of the hole injection layer, and preparing a blue light quantum dot light-emitting layer on the surface of one side, away from the hole injection layer, of the hole transport layer;
preparing an electron transport layer on the surface of one side, away from the hole transport layer, of the blue light quantum dot light-emitting layer, wherein the electron transport material for forming the electron transport layer comprises: red light quantum dot material, green light quantum dot material and inorganic electron transmission material;
and preparing a cathode on the surface of one side of the electron transmission layer, which is far away from the blue light quantum dot light-emitting layer.
11. The method for preparing a quantum dot device according to claim 10, wherein the preparing an electron transport layer on the surface of the blue light quantum dot light-emitting layer facing away from the hole transport layer comprises:
preparing an electron transport material solution comprising a red light quantum dot material, a green light quantum dot material and an inorganic electron transport material;
depositing the electron transport material solution on the surface of one side, away from the hole transport layer, of the blue light quantum dot light-emitting layer;
and annealing to obtain the electron transport layer.
12. The method for preparing a quantum dot device according to claim 10 or 11, wherein the annealing temperature is 80-170 ℃ and the annealing time is 5-60min; and/or
The thickness of the electron transmission layer is 0.05-5 um.
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