CN109980091A - A kind of Preparation method and use growing ZnO self-assembled nano structures - Google Patents

A kind of Preparation method and use growing ZnO self-assembled nano structures Download PDF

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CN109980091A
CN109980091A CN201910271637.7A CN201910271637A CN109980091A CN 109980091 A CN109980091 A CN 109980091A CN 201910271637 A CN201910271637 A CN 201910271637A CN 109980091 A CN109980091 A CN 109980091A
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zno
preparation
substrate
solution
nano structures
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纪文宇
戴棚棚
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Jilin University
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Jilin University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • 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]
    • H10K50/11—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a kind of Preparation method and uses of growth ZnO self-assembled nano structures of optoelectronic semiconductor technical field, have veining nanostructure and nano-scale figure spirit structure.Regulate and control film light transmittance or scattering effect by growing ZnO self-assembled nano structures in solution and substrate mixing interface, effectively reduce the total reflectivity between interface, improve the percent of pass of photon, dynamic process by synthesizing ZnO nanoparticle in solution grow on substrate textures the one or more of nanostructure and Tu Ling structure, applied to semiconductor photoelectric devices such as light emitting semiconductor device, solar battery and photodetectors, economic and practical is stronger.

Description

A kind of Preparation method and use growing ZnO self-assembled nano structures
Technical field
The present invention relates to semiconductor light electro-technical fields, specially a kind of to grow ZnO self-assembled nano structures in the solution Preparation method and use.
Background technique
Zinc oxide film refers to that group becomes the film of zinc oxide (ZnO).It has hexagonal prismoid shape wurtzite lattice structure, room The lower energy gap width of temperature is 3.3eV.
The current device in relation to semiconductor optoelectronic is due to flat and smooth between mutual interface, so the total reflection between interface Rate is higher, so that light takes out or utilization rate is lower, influences photoelectricity or electro-optical efficiency.
Summary of the invention
The purpose of the present invention is to provide a kind of Preparation method and uses for growing ZnO self-assembled nano structures, to solve Semiconductor photoelectric device related at present mentioned above in the background art due to flat and smooth between mutual interface, so interface it Between total reflectivity it is higher so that light takes out or utilization rate is lower, the problem of influencing photoelectricity or electro-optical efficiency.
To achieve the above object, the invention provides the following technical scheme: a kind of growth ZnO self-assembled nano structures, described Nanostructure is formed in the interface of substrate and solution mixing and is deposited on substrate.
Preferably, the ZnO self-assembled nano structures the preparation method is as follows:
Step 1: substrate is prepared；
Step 2: will contain Zr-based materials and alkali solute and dissolve respectively in a solvent, prepare solution containing Zr-based materials and Alkaline solution；
Step 3: solution containing Zr-based materials and alkaline solution are mixed with out by the volume ratio of 20:1 to 20:20 and mixed Solution is closed, then the substrate of preparation is contacted and reacted with the mixed solution, then is post-treated, obtains growing ZnO thin-film Nanostructure.
Preferably, the alkali solute is KOH, NaOH, LiOH or tetramethylammonium hydroxide.
Preferably, the content containing Zr-based materials in solvent solution is 1~25 (w/v) %, and the alkali solute exists Content in solvent solution is 0.1~20 (w/v) %.
Preferably, it reacts and is post-processed including heating and drying in the step 3, it is described to be heated to be at 25 DEG C~90 DEG C 1~30min of lower heating；The drying is to take off fire until the alcohol solvent evaporating completely on substrate.
Preferably, a kind of substrate of the step is glass substrate, silicon or silicon dioxide substrates, includes conduction on the substrate The semiconductor function layer film of film and organic or inorganic material.
Preferably, in the step 2 solvent be alcohol solvent or dimethyl sulfoxide any one.
Preferably, the conductive film includes the conductive metal films such as silver, aluminium, gold, copper, and indium tin oxide (ITO) is conductive The SnO of film, fluorine doped2Transparent conducting glass (FTO), the semiconductor function layer film include ZnO film, inorganic-quantum-dot Film and small organic molecule film.
Compared with prior art, the beneficial effects of the present invention are: passing through a kind of system for growing ZnO self-assembled nano structures Preparation Method and purposes, method design rationally, first prepare substrate, will contain Zr-based materials and alkali solute is dispersed or dissolved in alcohol respectively In property solvents, solution containing Zr-based materials and alkaline solution are prepared, Zr-based materials solution and alkaline solution will be contained by 20:1 to 20: 20 volume ratio mixing, then the substrate of preparation is contacted and is reacted with the mixed solution, in 25 DEG C~90 DEG C of temperature Degree is lower to be kept for 1~30 minute, is then taken out substrate drying, is obtained the nanostructure of growth ZnO self assembly, this kind of ZnO self assembly For nanostructure compared to the smooth structure between existing photoelectric device interface, this nanostructure smoothness is low, to reduce complete Reflectivity improves photon percent of pass, so as to be widely used in light emitting semiconductor device, solar battery and photodetection In the semiconductor photoelectric devices such as device.
Detailed description of the invention
Fig. 1 is present invention growth ZnO self-assembled nano structures nanostructure schematic diagram；
Fig. 2 is the optoelectronic semiconductor component structural schematic diagram that the present invention grows ZnO self-assembled nano structures in conductive electrode；
Fig. 3 is optoelectronic semiconductor component structural representation of the present invention in transport layer Material growth ZnO self-assembled nano structures Figure；
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
The invention provides the following technical scheme: a kind of preparation method and use of growing ZnO thin-film nanostructure in the solution On the way, for reducing the total reflectivity between interface, the percent of pass of photon is improved.
The present invention provides a kind of Preparation method and use for growing ZnO self-assembled nano structures:
Embodiment 1
Step 1: preparing ZnO film on a glass substrate, fire is then taken off on heating platform 30 minutes；
Step 2: Zr-based materials and alkali solute will be contained and be dissolved in alcohol solvent or dimethyl sulfoxide respectively, prepared Solution containing Zr-based materials and alkaline solution；
Step 3: solution containing Zr-based materials and alkaline solution are mixed by the volume ratio of 20:5, then by the ZnO of preparation Film-substrate is contacted and is reacted with the mixed solution；
Step 4: 50 DEG C at a temperature of kept for 5 minutes, it is dry to then take out ZnO film substrate, obtain growth ZnO from The film nano structure of assembling.
Wherein, the dry drying condition of ZnO film substrate is the temperature that 50 DEG C are heated on heating platform in step 4 Fire is taken off until alcohol solvent evaporating completely.
In the present embodiment, divide meter in proportion, growing ZnO thin-film nanostructure includes following composition to the one kind in the solution Ingredient:
ZnO film contains Zr-based materials, alkali solute and alcohol solvent, containing Zr-based materials in the solvent solution Content is 1 (w/v) %, and content of the alkali solute in the solvent solution is 0.1 (w/v) %, alkali solute KOH, is led to The dynamic process for crossing synthesis ZnO nanoparticle in solution grows one kind of veining nanostructure and Tu Ling structure on substrate Or it is a variety of.
The nanostructure generated by method made above is for improving light emitting semiconductor device, solar energy and photodetection The light transmittance and its scattering effect of device battery so as to improve photoelectric device performance.
Embodiment 2
Step 1: preparing ZnO film on a glass substrate, fire is then taken off on heating platform 30 minutes；
Step 2: Zr-based materials and alkali solute will be contained and be dissolved in alcohol solvent or dimethyl sulfoxide respectively, prepared Solution containing Zr-based materials and alkaline solution；
Step 3: solution containing Zr-based materials and alkaline solution are mixed by the volume ratio of 20:5, then by the ZnO of preparation Film-substrate is contacted and is reacted with the mixed solution；
Step 4: 60 DEG C at a temperature of kept for 20 minutes, it is dry to then take out ZnO film substrate, obtain growth ZnO from The film nano structure of assembling.
Wherein, the dry drying condition of ZnO film substrate is the temperature that 60 DEG C are heated on heating platform in step 4 Fire is taken off until alcohol solvent evaporating completely.
In the present embodiment, divide meter in proportion, growing ZnO thin-film nanostructure includes following composition to the one kind in the solution Ingredient:
ZnO film contains Zr-based materials, alkali solute and alcohol solvent, containing Zr-based materials in the solvent solution Content is 12.5 (w/v) %, and content of the alkali solute in the solvent solution is 10 (w/v) %, alkali solute NaOH, Dynamic process by synthesizing ZnO nanoparticle in solution grows the one of veining nanostructure and Tu Ling structure on substrate Kind is a variety of.
The nanostructure generated by method made above is for improving light emitting semiconductor device, solar energy and photodetection The light transmittance and its scattering effect of device battery so as to improve photoelectric device performance.
Embodiment 3
Step 1: preparing ZnO film on a glass substrate, fire is then taken off on heating platform 30 minutes；
Step 2: Zr-based materials and alkali solute will be contained and be dissolved in alcohol solvent or dimethyl sulfoxide respectively, prepared Solution containing Zr-based materials and alkaline solution；
Step 3: solution containing Zr-based materials and alkaline solution are mixed with mixed solution by the volume ratio of 20:5, so The ZnO film substrate of preparation is contacted and reacted with the mixed solution afterwards；
Step 4: 70 DEG C at a temperature of kept for 15 minutes, it is dry to then take out ZnO film substrate, obtain growth ZnO from The film nano structure of assembling.
Wherein, the dry drying condition of ZnO film substrate is the temperature that 70 DEG C are heated on heating platform in step 4 Fire is taken off until alcohol solvent evaporating completely.
In the present embodiment, divide meter in proportion, growing ZnO thin-film nanostructure includes following composition to the one kind in the solution Ingredient:
ZnO film contains Zr-based materials, alkali solute and alcohol solvent, containing Zr-based materials in the solvent solution Content is 25 (w/v) %, and content of the alkali solute in the solvent solution is 20 (w/v) %, alkali solute KOH, is led to The dynamic process for crossing synthesis ZnO nanoparticle in solution grows one kind of veining nanostructure and Tu Ling structure on substrate Or it is a variety of.
The nanostructure generated by method made above is for improving light emitting semiconductor device, solar battery and photoelectricity The light transmittance and its scattering effect of detector so as to improve photoelectric device performance.
Embodiment 4
Step 1: preparing ZnO film on a glass substrate, fire is then taken off on heating platform 30 minutes；
Step 2: Zr-based materials and alkali solute will be contained and be dissolved in alcohol solvent or dimethyl sulfoxide respectively, prepared Solution containing Zr-based materials and alkaline solution；
Step 3: solution containing Zr-based materials and alkaline solution are mixed with mixed solution by the volume ratio of 20:5, so The ZnO film substrate of preparation is contacted and reacted with the mixed solution afterwards；
Step 4: 80 DEG C at a temperature of kept for 15 minutes, it is dry to then take out ZnO film substrate, obtain growth ZnO from The film nano structure of assembling.
Wherein, the dry drying condition of ZnO film substrate is the temperature that 80 DEG C are heated on heating platform in step 4 Fire is taken off until alcohol solvent evaporating completely.
In the present embodiment, divide meter in proportion, growing ZnO thin-film nanostructure includes following composition to the one kind in the solution Ingredient:
ZnO film contains Zr-based materials, alkali solute and alcohol solvent, containing Zr-based materials in the solvent solution Content is 25 (w/v) %, and content of the alkali solute in the solvent solution is 20 (w/v) %, alkali solute NaOH, is led to The dynamic process for crossing synthesis ZnO nanoparticle in solution grows one kind of veining nanostructure and Tu Ling structure on substrate Or it is a variety of.
The nanostructure generated by method made above is for improving light emitting semiconductor device, solar energy and photodetection The light transmittance and its scattering effect of device battery so as to improve photoelectric device performance.
By number 1,2,3,4 respectively of nanostructure obtained by aforementioned four embodiment, to taken original in its production process The ratio of material is compared, while the nanostructure for using certain proportion to be produced it carries out light transmittance, reflectance Compare, referring specifically to following table:
In summary embodiment, a kind of growth ZnO self-assembled nano structures can effective solution at present in relation to semiconductor Photoelectric device leads to the higher problem of the total reflectivity between interface due to flat and smooth between mutual interface, improves light and penetrates Rate, while in the embodiment above, basic matterial selects the content range of KOH or NaOH, zinc ion in solvent solution 1 OH in~25 (w/v) %, alkali solute_Content range in solvent solution exists in 0.1~20 (w/v) %, heating time When between 5min~15min, adjustable nanostructure size parameter, thus ZnO nano-structure film prepared by regulation Reflecting effect and translucent effect, such method have compared to the ZnO film that chemical vapour deposition technique and magnetron sputtering method preparation generate Method is simple, characteristics easy to operate and at low cost etc..
Although hereinbefore having been made with reference to some embodiments, present invention is described, of the invention not departing from In the case where range, various improvement can be carried out to it and can be with equivalent without replacement component therein.Especially, as long as not There are structural conflict, the various features in presently disclosed each embodiment can be combined with each other by any way It uses, the description for not carrying out exhaustion to the case where these combinations in the present specification is only to be in omit length and economize on resources The considerations of.Therefore, the invention is not limited to specific embodiments disclosed herein, and including falling within the scope of the appended claims All technical solutions.

Claims (8)

1. a kind of growth ZnO self-assembled nano structures, it is characterised in that: the nanostructure be formed in substrate and solution mixing Interface is simultaneously deposited on substrate.
2. ZnO self-assembled nano structures according to claim 1 the preparation method is as follows:
Step 1: substrate is prepared；
Step 2: Zr-based materials and alkali solute will be contained and dissolved respectively in a solvent, solution containing Zr-based materials and alkalinity are prepared Solution；
Step 3: solution containing Zr-based materials and alkaline solution are mixed with out by the volume ratio of 20:1 to 20:20 mix it is molten Then the substrate of preparation is contacted and is reacted with the mixed solution by liquid, then post-treated, is obtained growth ZnO self assembly and is received Rice structure.
3. the preparation method of ZnO self-assembled nano structures according to claim 3, it is characterised in that: the alkali solute For KOH, NaOH, LiOH or tetramethylammonium hydroxide.
4. the preparation method of ZnO self-assembled nano structures according to claim 3, it is characterised in that: the material containing zinc-base Expect that the content in solvent solution is 1~25 (w/v) %, content of the alkali solute in solvent solution is 0.1~20 (w/ V) %.
5. the preparation method of ZnO self-assembled nano structures according to claim 2, it is characterised in that: in the step 3 Reaction and post-processing include heating and drying, described to be heated to be 1~30min of heating at 25 DEG C~90 DEG C；The drying is to take off Fire is until the alcohol solvent evaporating completely on substrate.
6. the preparation method of ZnO self-assembled nano structures according to claim 2, it is characterised in that: in the step 1 Substrate is glass substrate, silicon or silicon dioxide substrates, partly leading comprising conductive film and organic or inorganic material on the substrate Body function layer film.
7. the preparation method of ZnO self-assembled nano structures according to claim 2, it is characterised in that: in the step 2 Solvent be alcohol solvent or dimethyl sulfoxide any one.
8. the preparation method of ZnO self-assembled nano structures according to claim 5, it is characterised in that: the conductive film Include the conductive metal films such as silver, aluminium, gold, copper, the SnO of indium tin oxide (ITO) conductive film, fluorine doped2Transparent conducting glass (FTO), the semiconductor function layer film includes ZnO film, inorganic-quantum-dot film and small organic molecule film.
CN201910271637.7A 2019-04-04 2019-04-04 A kind of Preparation method and use growing ZnO self-assembled nano structures Pending CN109980091A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101320766A (en) * 2007-06-05 2008-12-10 台达电子工业股份有限公司 Current-diffusing layer, LED device and its preparing process
US20110189813A1 (en) * 2010-01-29 2011-08-04 Jenn Feng New Energy Co., Ltd. Method for fabricating copper/indium/gallium/selenium solar cell by wet process under non-vacuum condition
CN102190448A (en) * 2010-12-03 2011-09-21 中国科学院上海硅酸盐研究所 Composite broadband antireflecting film and preparation method thereof
CN102820396A (en) * 2007-06-05 2012-12-12 台达电子工业股份有限公司 Current diffusion layer, light emitting diode device and manufacturing method thereof
CN104009165A (en) * 2013-02-26 2014-08-27 海洋王照明科技股份有限公司 Organic electroluminescent device and preparation method
CN104743602A (en) * 2013-12-30 2015-07-01 神华集团有限责任公司 Hydrothermal synthesis method of zinc oxide nanomaterial and zinc oxide nanomaterial

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101320766A (en) * 2007-06-05 2008-12-10 台达电子工业股份有限公司 Current-diffusing layer, LED device and its preparing process
CN102820396A (en) * 2007-06-05 2012-12-12 台达电子工业股份有限公司 Current diffusion layer, light emitting diode device and manufacturing method thereof
US20110189813A1 (en) * 2010-01-29 2011-08-04 Jenn Feng New Energy Co., Ltd. Method for fabricating copper/indium/gallium/selenium solar cell by wet process under non-vacuum condition
CN102190448A (en) * 2010-12-03 2011-09-21 中国科学院上海硅酸盐研究所 Composite broadband antireflecting film and preparation method thereof
CN104009165A (en) * 2013-02-26 2014-08-27 海洋王照明科技股份有限公司 Organic electroluminescent device and preparation method
CN104743602A (en) * 2013-12-30 2015-07-01 神华集团有限责任公司 Hydrothermal synthesis method of zinc oxide nanomaterial and zinc oxide nanomaterial

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