CROSSLINKED NANOPARTICLE THIN FILM, PREPARATION METHOD THEREOF, AND THIN FILM OPTOELECTRONIC DEVICE HAVING THE SAME
20220367812 · 2022-11-17
Inventors
- Song CHEN (Huizhou, CN)
- Lei QIAN (Huizhou, CN)
- Yixing YANG (Huizhou, CN)
- Weiran CAO (Huizhou, CN)
- Chaoyu XIANG (Huizhou, CN)
Cpc classification
H01L21/02
ELECTRICITY
H10K30/00
ELECTRICITY
H10K30/35
ELECTRICITY
H10K10/488
ELECTRICITY
H01L31/1828
ELECTRICITY
H01L33/00
ELECTRICITY
H01L29/06
ELECTRICITY
International classification
Abstract
Disclosed is a preparation method for crosslinked nanoparticle film. The preparation method comprises: dispersing nanoparticles in a solvent and uniformly mixing same, so as to obtain a nanoparticle solution; and using the nanoparticle solution to prepare a nanoparticle thin film by means of a solution method, and introducing a gas combination to promote a crosslinking reaction, so as to obtain a crosslinked nanoparticle thin film. By introducing a gas combination during film formation of nanoparticles, the present disclosure promotes the crosslinking among particles, and thus increases the electrical coupling among particles, lowers the potential barrier of carrier transmission, and increases the carrier mobility, thereby greatly improving the electrical properties of the thin film.
Claims
1. A method for preparing crosslinked nanoparticle thin film, comprising: mixing nanoparticles with a solvent to form a mixture; obtaining a nanoparticle solution by stirring the mixture to uniformly disperse the nanoparticles in the mixture; preparing a nanoparticle thin film from the nanoparticle solution by a solution method; and introducing a gas mixture into an environment having the nanoparticle thin film to obtain a crosslinked nanoparticle thin film, the gas mixture promoting the crosslinking reactions of the nanoparticles.
2. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the gas mixture comprises a reduced gas, oxygen, water vapor and carbon dioxide.
3. The method for preparing crosslinked nanoparticle thin film according to claim 2, wherein a bias pressure for the reduced gas is between 1 and 100 Pa, a bias pressure for the oxygen is between 0 and 2×10.sup.4 Pa, a bias pressure for the water vapor is between 0 and 2×10.sup.3 Pa, and a bias pressure for the carbon dioxide is between 0 and 100 Pa.
4. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the nanoparticle solution has a mass concentration of 1 to 100 mg/ml.
5. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the nanoparticles are one or more of: oxide nanoparticles, sulfide nanoparticles, selenide nanoparticles, nitride nanoparticles, and fluoride nanoparticles.
6. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein an average diameter of the nanoparticles is within 5 nm.
7. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the solvent is an alcohol solvent.
8. The method for preparing crosslinked nanoparticle thin film according to claim 2, wherein the reduced gas is one of: carbon monoxide, hydrogen, and ammonia.
9. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the crosslinked nanoparticle film has a thickness of 15 to 60 nm.
10. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the nanoparticle thin film is prepared from the nanoparticle solution by a solution method in a closed environment and/or an inert atmosphere and the environment having the nanoparticle thin film is a closed environment.
11. The method for preparing crosslinked nanoparticle thin film according to claim 1, wherein the solution method is a chemical solution deposition for fabricating thin films, wherein a solution is deposited on a substrate via spin coating, ink jet printing, spray coating, or blade coating.
12. An electroluminescent device, comprising a first electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a second electrode, wherein a material of the electron transport layer is a crosslinked nanoparticle thin film prepared by the method according to claim 1.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE EMBODIMENTS
[0043] The present disclosure provides a crosslinked nanoparticle film, a preparation method thereof and a thin film optoelectronic device. The present disclosure will be further described in detail below in order to make the objects, technical solutions and effects of the present disclosure clear. It is understood that the specific embodiments described herein are merely illustrative examples of the present disclosure and do not limit the present disclosure.
[0044] An embodiment of the present disclosure provides a method for preparing a crosslinked nanoparticle thin film, wherein the method includes:
[0045] Step A: Dispersing nanoparticles in a solvent and uniformly mix the nanoparticles and the solvent, to obtain a nanoparticle solution.
[0046] Specifically, the step A includes: Dispersing the nanoparticles in a solvent at a mass concentration of 1 to 100 mg/ml, mix uniformly, to obtain a nanoparticle solution used for film formation by solution methods. The nanoparticles may be one or more of wide band-gap oxide nanoparticles, sulfide nanoparticles, selenide nanoparticles, nitride nanoparticles, and fluoride nanoparticles. The oxide nanoparticles may be, but not limited to one of ZnOx (e.g., ZnO), TiOx (e.g., TiO.sub.2), etc. The sulfide nanoparticles may be, but not limited to, one of zinc sulfides and molybdenum sulfides. The selenide nanoparticles may be, but are not limited to, one of zinc selenides and lead selenides. The nitride nanoparticles may be, but not limited to, one of silicon nitrides and aluminum nitrides. The fluoride nanoparticles may be, but not limited to, one of lanthanum fluorides and sodium fluorides. In the present disclosure, the dimension of the nanoparticles may be controlled. The average diameter of the spherical nanoparticles may be limited to within 5 nm, to ensure that a sufficient amount of surface state metal atoms can participate in the reactions. The solvent may be an alcohol solvent such as a methanol, an ethanol, etc.
[0047] Step B: Preparing nanoparticle thin films by a solution method; and introducing a gas mixture to promote cross-linking reactions to obtain crosslinked nanoparticle thin films. In the present disclosure, a solution method to deposit thin films is provided, the solution method may be spin coating, ink jet printing, spray coating, or blade coating, etc.
[0048] Specifically, the gas mixture includes: a reduced gas, an oxygen, water vapor, and carbon dioxide. Preferably, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled between 0 and 2×10.sup.4 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. According to the present disclosure, the bias pressure of the gas mixture in contact with thin films is controlled. Preferably, such bias pressure of each gas is controlled within the above-described ranges, because the density of thin film prepared under such bias pressure ranges is higher, and accordingly, the carrier mobility in the thin films is also higher.
[0049]
[0050] The conditions for crosslinking reactions for each of the above type of nanoparticles will be described in detail below.
1. Oxide Nanoparticle
[0051] When the nanoparticles are zinc oxide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled between 0 and 1×10.sup.3 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. The density of thin films prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
[0052] When the nanoparticles are titanium oxide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled between 0 and 1×10.sup.4 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. The density of thin films prepared under such bias ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
[0053] When the nanoparticles are nickel oxide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; and the oxygen bias pressure is controlled between 0 and 5×10.sup.3 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 P; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. The density of thin films prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
2. Sulfide Nanoparticles
[0054] When the nanoparticles are zinc sulfide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. The density of thin films prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
[0055] When the nanoparticles are molybdenum sulfide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. The density of thin film under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
3. Selenide Nanoparticles
[0056] When the nanoparticles are zinc selenide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled between 0 and 1×10.sup.2 Pa; and the carbon dioxide bias pressure is controlled between 0 and 10 Pa. The density of thin films produced under this bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
[0057] When the nanoparticles are lead selenide nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled to be less than 0.1 Pa, carbon dioxide bias pressure is controlled between 0 and 100 Pa. The density of thin films produced under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
4. Nitride Nanoparticles
[0058] When the nanoparticles are silicon nitride nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled at 0.1 and 1 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 0 and 100 Pa. Additionally, the nitrogen gas bias pressure is maintained at about 1×10.sup.5 Pa. The density of thin films prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in thin films is also higher.
[0059] When the nanoparticles are aluminum nitride nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias pressure is controlled between 10 and 100 Pa. Additionally, the nitrogen gas bias pressure is maintained at about 1×10 5 Pa. The density of thin film prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
5. Fluoride Nanoparticles
[0060] When the nanoparticles are lanthanum fluoride nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled between 0 and 1×10.sup.2 Pa; and the carbon dioxide bias pressure is controlled between 0 and 10 Pa. The density of thin films prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
[0061] When the nanoparticles are sodium fluoride nanoparticles, the reduced gas (e.g., carbon monoxide, hydrogen or ammonia) bias pressure is controlled between 1 and 100 Pa; the oxygen bias pressure is controlled to be less than 0.1 Pa; the water vapor bias pressure is controlled between 0 and 2×10.sup.3 Pa; and the carbon dioxide bias is controlled between 10 and 100 Pa. The density of thin films prepared under such bias pressure ranges is higher, and accordingly, the carrier electron mobility in the thin films is also higher.
[0062] In the present disclosure, the nanoparticles are crosslinked during thin film formation. Cross-links are chemical bonds that connect nanoparticles, among which there are fillers. In contrast, there is no material linked by chemical bonds between the uncrosslinked nanoparticles. The crosslinking method of the present disclosure can increase the density and carrier mobility in the corresponding thin films.
[0063] In the present disclosure, nanoparticle films can be prepared directly from a nanoparticle solution under a non-vacuum condition. Specifically, the step B includes:
[0064] Step B1: Placing a nanoparticle solution in a closed environment, and preparing nanoparticle thin films by a solution method; and
[0065] Step B2: Introducing a gas mixture into the closed environment, to promote crosslinking reactions, to obtain crosslinked nanoparticles.
[0066] In the foregoing described embodiments, nanoparticle thin films are prepared from a nanoparticle solution under a closed non-vacuum condition. The above-mentioned gas mixture is then introduced to the closed environment, to promote crosslinking reactions, to obtain crosslinked nanoparticle thin films.
[0067] The preparation of crosslinked nanoparticle thin films of the present disclosure is not limited to the above-mentioned environment. The nanoparticle thin films can be prepared under an inert atmosphere, and then be placed in a closed environment. The closed environment is then introduced a gas mixture, to promote the crosslinking reactions, to obtain nanoparticle thin films. Specifically, the Step B includes:
[0068] Step B1′: Placing the nanoparticle solution in an inert atmosphere and preparing nanoparticle thin films by a solution method; and
[0069] Step B2′: Placing the nanoparticle thin film in a closed environment, and introducing a gas mixture into the closed environment, to promote crosslinking reactions, to obtain crosslinked nanoparticle thin films.
[0070] In the present disclosure, after the crosslinking reactions, the crosslinked nanoparticle thin films are dried to finally obtain crosslinked nanoparticle thin film having a thickness of 15 to 60 nm. The drying temperature is higher than the boiling point of the solvent in the nanoparticle solution; according to the thickness of the film, the drying time is more than 15 minutes per 50 nm.
[0071] The present disclosure also provides a crosslinked nanoparticle thin films prepared by any of the above methods for preparing crosslinked nanoparticle thin films.
[0072] Usually, a nanoparticle thin film is self-assembled from nanoparticles that are not crosslinked to each other. In the present disclosure, during thin film formation of the nanoparticles, a gas mixture is introduced to promote crosslinking among the particles, thereby increasing electrical coupling between the particles, reducing the transport barrier of carriers, increasing carrier mobility, and accordingly, improving the electrical performance. The application of the obtained crosslinked nanoparticle thin films in light-emitting diodes, thin film solar cells, light detectors, and thin film transistors prepared by solution methods can significantly improve the performance of these devices.
[0073] Below is an illustrative example of zinc oxide nanoparticles, and the properties of the existing uncrosslinked zinc oxide nanoparticle thin films and the properties of the crosslinked zinc oxide nanoparticle thin films prepared by the methods of the present disclosure are tested. Referring to
[0074] The present disclosure also provides a thin film optoelectronic device, wherein, the thin film optoelectronic device includes a crosslinked nanoparticle thin film. Specifically, the thin film optoelectronic device is any one of: an electroluminescent device, a thin film photovoltaic device, a thin film light detector, and a thin film transistor.
[0075] As a specific embodiment of the optoelectronic thin film device, as shown in
[0076] In the electroluminescent device of the present embodiment, at least one of the first electrode and the second electrode has high light transmittance for a light band emitted by the light emitting layer. Specifically, the material for the first electrode is selected from one or more of: indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony doped tin oxide (ATO), aluminum-doped zinc oxide (AZO); preferably, the first electrode is an ITO electrode.
[0077] Further, in the present embodiment, the material for the hole transport layer 430 is selected from the materials or the materials with the chemical groups: poly[bis(4-phenyl)(4-butylphenyl)amine], 4-butyl-N,N-diphenylaniline homopolymer, aniline, 4-butyl-N,N-diphenyl, homopolymer (poly-TPD), poly(9,9-dioctylfluorene-CO—N-(4-butylphenyl)-diphenylamine) (TFB), poly(9-vinylcarbazole) (PVK), TPD, Spiro-TPD, LG101, HAT-CN, PEDOT: PSS, TAPC, a-NPB, m-MTDATA, Ni.sub.xO, MoO.sub.x, VO.sub.x, WO.sub.x and a mixture thereof; preferably, the hole transport layer 30 is a poly-TPD layer and has a thickness of 10 to 100 nm.
[0078] Further, in the present embodiment, the material for the quantum dot light-emitting layer includes but not limited to: nanocrystals of II-VI semiconductor, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe and other binary, ternary, or quaternary II-VI compounds; III-V semiconductor nanocrystals, for example, GaP, GaAs, InP, InAs or other binary, ternary, or quaternary III-V compounds. The quantum dot luminescent material for electroluminescence is not limited to II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compound, or group IV elements.
[0079] Further, in the present embodiment, the material for the second electrode is selected from: Al, Ag, Cu, Mo, Au, or an alloy thereof; preferably, the material for the second electrode is Au. The second electrode has a thickness of 50 to 500 nm; preferably, the second electrode has a thickness of 100 to 200 nm.
[0080] As a specific embodiment of the thin film optoelectronic device, as shown in
[0081] In the present embodiment of the thin film photovoltaic device, at least one of the first electrode and the second electrode has high sunlight transmittance. Specifically, the first electrode is selected from one or more of: indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO); preferably, the material for the first electrode is ITO.
[0082] Further, according to the present embodiment, the light absorbing layer may be a semiconductor homojunction or a heterojunction. The material for the light absorbing layer is a light absorbing material in a solar spectrum, and may include: polymer photovoltaic material; organic small molecule photovoltaic material; halogen-containing perovskite photovoltaic material; chalcopyrite structural material (e.g., copper indium gallium selenide); II-VI compound material (e.g., thin films and nanocrystals); single crystal, polycrystalline, or amorphous silicon. If the light absorbing layer is a homojunction, the light absorbing layer includes a specific material of one material category from above; if the light absorbing layer is a heterojunction, the light absorbing layer includes two specific materials from one or two material categories from above.
[0083] Further, in the present embodiment, the material for the second electrode is selected from: Al, Ag, Cu, Mo, Au, or an alloy thereof; preferably, the material for the second electrode is Au. The second electrode has a thickness of 50 to 500 nm; preferably, the second electrode has a thickness of 100 to 200 nm.
[0084] As a specific embodiment of the thin film optoelectronic device, as shown in
[0085] According to the present embodiment of the thin film light detector, at least one of the anode and the cathode has high transmittance for the detection band.
[0086] Further, in the present embodiment, the material for the anode is selected one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO); preferably, the material for the anode is ITO.
[0087] Further, in the present embodiment, the material for the electron blocking layer is selected from: poly(9,9-dioctylfluorene-CO—N-(4-butylphenyl)-diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N′ bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine) (poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4′,4″-tris(carbazol-9-yl)-triphenylamine (TCTA), 4,4′-bis(9-carbazole)-biphenyl (CBP), N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine (TPD), N,N′-diphenyl-N,N′-(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (NPB), doped graphene, undoped graphene, C60, or a mixture thereof; preferably, the material for the electron blocking layer 5 is poly-TPD. The electron blocking layer 620 has a thickness of 10 to 100 nm.
[0088] Further, in the present embodiment, the material for the light absorbing layer is one or more of: a binary III-V compound (e.g., GaN, GaAs or InGaAs); a multinary III-V compound; a nanocrystal of a II-VI compound material, an organic semiconductor material; a halogen-containing perovskite material; a chalcopyrite structural material (e.g., copper indium gallium selenide); a single crystal, polycrystalline, or amorphous silicon. The light absorbing layer (photoelectron generating layer) may be a semiconductor homojunction or a semiconductor heterojunction. Specifically, in some embodiments, if the light absorbing layer is a homojunction, the material for the light absorbing layer is one specific material of a material category from above. Specifically, if the light absorbing layer is a heterojunction, the material for the light absorbing layer are two specific materials of one or two material category from above.
[0089] Further, in the present embodiment, the cathode material is selected from: Al, Ag, Cu, Mo, Au, or an alloy thereof; preferably, the cathode material is Au. The cathode has a thickness of 50 to 500 nm. In some embodiments, the cathode has a thickness of 100 to 200 nm; preferably, the thin film light detector is partially packaged, fully packaged, or unpackaged.
[0090] As a specific embodiment of the thin film optoelectronic device, as shown in
[0091] Further, as shown in
[0092] Or, as shown in
[0093] In the present embodiment of the thin film transistor, the material for the source electrode, the drain electrode, and the gate electrode may be a metal or a semiconductor having high conductivity. The material for the insulating layer may be a dielectric material, for example, an oxide, or a nitride.
[0094] In summary, the present disclosure provides a crosslinked nanoparticle thin film, a preparation method thereof and a thin film optoelectronic device. In the present disclosure, a gas mixture is introduced during the nanoparticle thin film formation, to promote crosslinking among the particles, which increases the electrical coupling between the particles, reduces the transport barrier of carriers, increases the carrier mobility, and accordingly, greatly improves the electrical performance. The application of the obtained crosslinked nanoparticle thin films in electroluminescent device prepared by solution methods, as electron transport layer, can apparently improve carrier balance, luminous efficiency and lifetime of the device. The application of the obtained crosslinked nanoparticle thin films in photovoltaic devices prepared by solution methods, as electron transport layer, can significantly reduce the linear resistance of the device, improve the parallel resistance, and improve the energy conversion efficiency of the device. The application of the obtained crosslinked nanoparticle thin films in thin film light detector prepared by solution methods, as electron extraction layer and hole blocking layer, can reduce the current and improve the detection rate. The application of the obtained crosslinked nanoparticle thin films in thin film transistor prepared by solution methods, can improve the carrier mobility of the semiconductor layer, increase the source-drain current, and increase the response frequency.
[0095] It is to be understood that the application of the present disclosure is not limited to the foregoing described examples, and those skilled in the art can make modifications and variations in accordance with the above descriptions, all of which are within the scope of the appended claims.