CN104761154B - A kind of method that utilization organic macromolecule material makees catalyst preparation ITO nano wires - Google Patents

A kind of method that utilization organic macromolecule material makees catalyst preparation ITO nano wires Download PDF

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CN104761154B
CN104761154B CN201510094494.9A CN201510094494A CN104761154B CN 104761154 B CN104761154 B CN 104761154B CN 201510094494 A CN201510094494 A CN 201510094494A CN 104761154 B CN104761154 B CN 104761154B
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ito
nano wires
macromolecule material
organic macromolecule
ito nano
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CN104761154A (en
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云峰
李虞锋
弓志娜
郭茂峰
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The present invention discloses a kind of method that ITO nano wires are directly prepared by the use of organic macromolecule material as catalyst, this method deposits individual layer polystyrene sphere using the method for self assembly on substrate first, polystyrene sphere is carried out to the preparation of ITO nano wires as catalyst followed by the mode of electron beam evaporation plating, then polystyrene is removed using chloroform cleaning or annealing way, so as to obtain the acicular ITO nano wire that large area is evenly distributed.The present invention carries out the preparation method of ITO nano wires using organic macromolecule material as catalyst, it is simple with material requested cheap (low cost), low temperature (280~320 DEG C), operating procedure, easily prepared the features such as, prepare the ITO nanowire lengths completed and can reach micron dimension, needle-like is presented in end, it is thermally-stabilised good, there are good electric conductivity and light transmission, there is stronger application value in terms of FED, nano-sensor, LED and solar cell.

Description

A kind of method that utilization organic macromolecule material makees catalyst preparation ITO nano wires
【Technical field】
The invention belongs to opto-electronic device field of material technology, the side of ITO (tin indium oxide) nano wire is more particularly to prepared Method.
【Background technology】
ITO materials have good chemical stability and heat endurance, and there is good tack and figure to carve to substrate Characteristic is lost, a kind of mature LED applied to horizontal structure of transparent conductive film is used as.Add plating in the LED of horizontal structure ITO material layers, can make the electric current of injection LED chip quick and uniformly spread, increase electronics enlivens performance, to reach lifting The purpose of LED light conversion efficiency.ITO materials after annealing have good electric conductivity and oxidation resistance, can be used as field The cold-cathode material of transmitting.ITO materials have very high gas-sensitive property to predetermined substance (such as ethanol) simultaneously, can also answer For sensor field.Excellent conductivity at room temperature performance, the transmitance of visible ray and distinctive are had based on ITO materials simultaneously Gas-sensitive property, has obtained extensive research and application in recent years.
Nano thread structure has been widely used in electricity due to its high surface-volume ratio and excellent electricity, thermal characteristics The fields such as son, photoelectron, chemical/biological sensors, energy harvesting/conversion.From 1964, gas-liquid-solid (VLS) growth mechanism Since by Wagner and Ellis discoveries, many innovative methods, such as chemical vapour deposition technique, molecular beam epitaxy have been occurred in that Deng greatly having promoted the synthesis and application of nano wire.Not only the characteristic with nanostructured also maintains ITO body materials to ITO nano wires The high transmitance of material and the advantage of electric conductivity, can be effectively applied in solar cell, display, plasma and LED hair Optical device.For preparing ITO nano wires, technology common at present is to be entered based on VLS mechanism by the use of metal (gold) as catalyst Row prepares [C.O ' Dwyer, M.Szachowica G.Visimberga, et.al, Nature Nanotech., 4,239 (2009) the factor restriction such as], this method has temperature high (800~900 DEG C), cost high and manufacture craft is more complicated, it is difficult to Realize mass produce simultaneously apply, and after ITO nano wires are prepared how effectively and thoroughly go metallic particles also to turn into One problem.
In order to solve the related problem in prepared by ITO nano wires, retrieval finds that method prepared by different ITO nano wires is The Chinese patent of application has:Application No. 200610031534.6 and 200910024491.2.But pass through analysis, application Number still used using metal -- Au as catalyst progress ITO nano wires for 200610031534.6 patent application Prepare, the problem of fundamentally solving catalyst cost height and be difficult to remove;And Application No. 200910024491.2 Patent application uses a kind of mode of electron beam evaporation plating and directly prepares ITO nano wires, it is desirable to the control technique of equipment compared with Harshness, and the ITO nanowire lengths prepared can only be at nanometer scale (~100nm), pattern control is second-rate.
【The content of the invention】
Make the method that catalysis prepares ITO nano wires it is an object of the invention to provide a kind of utilization organic macromolecule material, To solve the problem of above-mentioned prior art is present.The inventive method makes its conduct by coating polystyrene sphere on substrate Catalyst, directly utilizes electron beam evaporation plating mode, realizes that preparing needle-like ITO nanowire lengths reaches micron dimension (~2 μm) It is prepared by low cost and large area.
To achieve these goals, the present invention is adopted the following technical scheme that:
A kind of utilization organic macromolecule material makees the method that catalysis prepares ITO nano wires, comprises the following steps:
Polystyrene sphere array is prepared on substrate, ICP etchings is carried out with oxygen polystyrene sphere is modified;
ITO evaporations are carried out to the substrate for being coated with polystyrene sphere;
The substrate leaching that ITO completions are deposited is removed to the polystyrene of residual by the way of chloroform immersion or high annealing, Obtain ITO nano wires.
It is preferred that, individual layer polystyrene sphere array is prepared on substrate.
It is preferred that, a diameter of 500nm of polystyrene sphere.
It is preferred that, when carrying out ITO evaporations, underlayer temperature is maintained at 280~320 degrees Celsius, and substrate is attached with into polyphenyl second The one side of alkene bead is just to target, by 0.08~0.1nm/s sedimentation rate, and deposition stops evaporation, cooling after 15~20 minutes After take out substrate.
It is preferred that, when ITO is deposited, polystyrene sphere is in molten condition.
It is preferred that, when ITO is deposited, using In:Sn=90:10 target;Vacuum pressure is less than 5 × 10 in evaporation cavity-4Pa。
It is preferred that, the substrate is quartz glass plate or GaN epitaxy piece.
It is preferred that, high-temperature annealing process is:Annealed 10~15 minutes under 570~600 degrees Celsius using quick anneal oven, Remove polystyrene sphere.
It is preferred that, during high annealing from room temperature to the heating rate of annealing temperature be 100 DEG C/s, the cooling after annealing Speed is 80 DEG C/s.
Relative to prior art, the invention has the advantages that:
In the present invention, when being coated with the quartz glass substrate of polystyrene sphere in the range of 280~320 DEG C of temperature, Polystyrene sphere is in molten condition.When ITO target molecular vapor (tin oxide, indium oxide mixed gas molecule) is on substrate During deposition, the polystyrene sphere in molten state has stronger absorption and adhesive ability, high temperature ITO molecules to ITO molecules Constantly assemble in the polystyrene sphere of molten state, when reaching supersaturation, just outwards separated out in the way of crystallization, formed The ITO nano wires of needle-like.
In the present invention, it is catalyzed using organic macromolecule material, size and density all have good controllability, Ke Yigen Selected according to demand.It is easier to remove, and noresidue.ITO evaporation rates and underlayer temperature can be regulated and controled simultaneously, tested With temperature it is low, consume energy less, it is prepared by controllable ITO nanowire sizes, free from admixture and large area the features such as.
Further experiment proves, makees to be catalyzed the ITO nano wires prepared with organic macromolecule material, with certain in diameter In the case of, the continuous growth of length can be achieved, micron dimension is reached.And ITO nano wires prepared by the present invention pass through at 600 DEG C Can be than more completely keeping original pattern after lower annealing, with good electric conductivity and light transmission, this characteristic is sent out in LED There is stronger application value in terms of optical device and solar cell.
In the present invention, make to be catalyzed the ITO nano wires prepared using organic macromolecule material, with the increase of length, ITO receives Rice noodles end diameter is tapered into until being changed into tip-like, and the ITO nano wires of this pattern have significant field emission performance, this Characteristic has preferable application prospect in terms of FED.
It is proposed by the present invention to do the method that catalysis large area prepares ITO nano wires using a kind of organic macromolecule material, have What is imitated reduces experimental cost, and simple to operate, preparation technology is succinct, and energy consumption is low and yield is high, and stability is good, nanocrystalline It will be widely applied in terms of solar cell, nano-sensor and LED light electroluminescence device.
【Brief description of the drawings】
Fig. 1 is the process schematic diagram that the inventive method prepares ITO nano wires.
Fig. 2 is field emission scanning electron microscope (SEM) figure of polystyrene sphere.
After the completion of Fig. 3 is evaporation ITO, the ITO nano wire Flied emission scanning electron microscopies of polyphenylacetylene catalyst are not removed Mirror (SEM) figure.
Fig. 4 is that the ITO nano wires field emission scanning electron microscope (SEM) after polyphenylacetylene catalyst is got rid of with chloroform Figure.
Fig. 5 is that the ITO nano wire field emission scanning electron microscopes after polyphenylacetylene catalyst are got rid of with annealing way (SEM) figure.
【Embodiment】
Embodiment 1
Refer to shown in Fig. 1, a kind of utilization organic macromolecule material of the invention makees the method that catalysis prepares ITO nano wires, Comprise the following steps:The GaN epitaxy piece of one 2 inches diameter is respectively put into acetone, ethanol (99.7%) solvent at room temperature It is cleaned by ultrasonic 10 minutes, is then dried up with nitrogen after deionized water rinsing.Self assembly is deposited on the GaN epitaxy piece cleaned up A diameter of 500nm individual layer polystyrene sphere, depositional area covers whole substrate, uses field emission scanning electron microscope (SEM) sample surfaces are observed, result as shown in Figure 2 is obtained.After carrying out ICP etchings 200 seconds with oxygen afterwards, then carry out SEM Observation, obtain the result as shown in illustration in Fig. 2, it can be seen that polystyrene sphere surface is modified, and bead it Between spacing increase.
The GaN epitaxy piece for being attached with polystyrene sphere is put on the specimen holder of electron-beam coating equipment, there is polyphenyl second The one side of alkene bead is just to ITO target.Load ITO target (In:Sn=90:10) after, evaporation cavity chamber door is closed, progress is taken out true Sky, makes vacuum pressure in cavity be less than 5 × 10-4Pa, is heated to target and specimen holder, and temperature makes polystyrene at 300 DEG C There is the state melted in bead.Beam spot is adjusted, target is deposited after evaporating on GaN epitaxy piece.Electron beam is adjusted afterwards Line, makes sedimentation rate in the range of 0.08~0.1nm/s, carries out vapor deposition after 15 minutes, stops evaporation, is taken out after cooling GaN epitaxy piece, is observed by field emission scanning electron microscope, can obtain result as shown in Figure 3, and illustration is a polyphenyl The result figure of ITO nano wires is grown on ethene bead.As can be seen from the figure ITO nano wires are interweaved, and diameter is left in 15nm The right side, most long reachable~2 μm, ITO nanowire ends presentation tip-like of length.
The GaN epitaxy piece immersion chloroform (CHCl for there are ITO nano wires will be grown3) ultrasound 30 minutes in solution, for thorough Remove polyphenylacetylene catalyst.Then deionized water rinsing is used, it is aobvious by Flied emission scanning electron after drying naturally in atmosphere Micro mirror is observed, and can obtain result as shown in Figure 4.It can be seen that polystyrene is all removed, ITO nanometers of line morphologies are simultaneously Do not change, and be distributed than more uniform.
Embodiment 2
The ITO evaporations of GaN epitaxy piece are completed according to step in case study on implementation 1, annealing furnace (rapid alloying is then put it into Stove, model:RTP-3,100 DEG C/s of programming rate, 80 DEG C/s of cooling rate) in set annealing temperature be 600 DEG C, adjust nitrogen stream Measure as 25ml/min, carry out annealing 10 minutes, substrate is taken out after cooling, carry out field emission scanning electron microscope observation, can To obtain result as shown in Figure 5.It can be seen that ITO nano wires pattern after high annealing remains unchanged and kept intact, and possess good Electric conductivity and light transmission.
Embodiment 3
Refer to shown in Fig. 1, a kind of utilization organic macromolecule material of the invention makees the method that catalysis prepares ITO nano wires, Comprise the following steps:The GaN epitaxy piece of one 2 inches diameter is respectively put into acetone, ethanol (99.7%) solvent at room temperature It is cleaned by ultrasonic 10 minutes, is then dried up with nitrogen after deionized water rinsing.Self assembly is deposited on the GaN epitaxy piece cleaned up A diameter of 500nm individual layer polystyrene sphere, depositional area covers whole substrate.ICP is carried out with oxygen afterwards to etch 200 seconds Polystyrene sphere surface is modified, and increases the spacing between bead.
The GaN epitaxy piece for being attached with polystyrene sphere is put on the specimen holder of electron-beam coating equipment, there is polyphenyl second The one side of alkene bead is just to ITO target.Load ITO target (In:Sn=90:10) after, evaporation cavity chamber door is closed, progress is taken out true Sky, makes vacuum pressure in cavity be less than 5 × 10-4Pa, is heated to target and specimen holder, and temperature makes polyphenyl second at 280 DEG C There is the state melted in alkene bead.Beam spot is adjusted, target is deposited after evaporating on GaN epitaxy piece.Electronics is adjusted afterwards Beam line, makes sedimentation rate in the range of 0.08~0.1nm/s, carries out vapor deposition after 20 minutes, stops evaporation, taken after cooling Go out GaN epitaxy piece.
The GaN epitaxy piece immersion chloroform (CHCl for there are ITO nano wires will be grown3) ultrasound 30 minutes in solution, for thorough Remove polyphenylacetylene catalyst.
Embodiment 4
The ITO evaporations of GaN epitaxy piece are completed according to step in case study on implementation 3, annealing furnace (rapid alloying is then put it into Stove, model:RTP-3,100 DEG C/s of programming rate, 80 DEG C/s of cooling rate) in set annealing temperature be 570 DEG C, adjust nitrogen stream Measure as 25ml/min, carry out annealing 10 minutes, substrate is taken out after cooling, ITO nano wires are obtained.
Embodiment 5
Refer to shown in Fig. 1, a kind of utilization organic macromolecule material of the invention makees the method that catalysis prepares ITO nano wires, Comprise the following steps:The GaN epitaxy piece of one 2 inches diameter is respectively put into acetone, ethanol (99.7%) solvent at room temperature It is cleaned by ultrasonic 10 minutes, is then dried up with nitrogen after deionized water rinsing.Self assembly is deposited on the GaN epitaxy piece cleaned up A diameter of 500nm individual layer polystyrene sphere, depositional area covers whole substrate.ICP is carried out with oxygen afterwards to etch 200 seconds Polystyrene sphere surface is modified, and increases the spacing between bead.
The GaN epitaxy piece for being attached with polystyrene sphere is put on the specimen holder of electron-beam coating equipment, there is polyphenyl second The one side of alkene bead is just to ITO target.Load ITO target (In:Sn=90:10) after, evaporation cavity chamber door is closed, progress is taken out true Sky, makes vacuum pressure in cavity be less than 5 × 10-4Pa, is heated to target and specimen holder, and temperature makes polystyrene at 320 DEG C There is the state melted in bead.Beam spot is adjusted, target is deposited after evaporating on GaN epitaxy piece.Electron beam is adjusted afterwards Line, makes sedimentation rate in the range of 0.08~0.1nm/s, carries out vapor deposition after 18 minutes, stops evaporation, is taken out after cooling GaN epitaxy piece.
The GaN epitaxy piece immersion chloroform (CHCl for there are ITO nano wires will be grown3) ultrasound 30 minutes in solution, for thorough Remove polyphenylacetylene catalyst.
Embodiment 6
The ITO evaporations of GaN epitaxy piece are completed according to step in case study on implementation 5, annealing furnace (rapid alloying is then put it into Stove, model:RTP-3,100 DEG C/s of programming rate, 80 DEG C/s of cooling rate) in set annealing temperature be 580 DEG C, adjust nitrogen stream Measure as 25ml/min, carry out annealing 12 minutes, substrate is taken out after cooling, ITO nano wires are obtained.
It can be seen from above example, the present invention has been prepared by the use of a kind of organic macromolecule material as catalyst The large area ITO nano wires of even needle-like, the features such as possessing low temperature (300 DEG C or so), low cost, simple operating steps.

Claims (5)

1. a kind of method that utilization organic macromolecule material makees catalyst preparation ITO nano wires, it is characterised in that including following step Suddenly:
Polystyrene sphere array is prepared on substrate, ICP etchings is carried out with oxygen polystyrene sphere is modified;
ITO evaporations are carried out to the substrate for being coated with polystyrene sphere;When carrying out ITO evaporations, underlayer temperature is maintained at 280~ 320 degrees Celsius, polystyrene sphere is set to be in molten state;By 0.08~0.1nm/s sedimentation rate, deposit 15~20 minutes Afterwards, stop evaporation, substrate is taken out after cooling;
The substrate that ITO completions are deposited is removed to the polystyrene of residual by the way of chloroform immersion or high annealing, obtains pure Net ITO nano wires;Tip-like is presented in ITO nanowire ends.
2. the method that a kind of utilization organic macromolecule material according to claim 1 makees catalyst preparation ITO nano wires, its It is characterised by, a diameter of 500nm of polystyrene sphere.
3. the method that a kind of utilization organic macromolecule material according to claim 1 makees catalyst preparation ITO nano wires, its It is characterised by, when ITO is deposited, using In:Sn=90:10 target;Vacuum pressure is less than 5 × 10 in evaporation cavity-4Pa。
4. the method that a kind of utilization organic macromolecule material according to claim 1 makees catalyst preparation ITO nano wires, its It is characterised by, high-temperature annealing process is:Annealed 10~15 minutes, removed poly- under 570~600 degrees Celsius using quick anneal oven Styrene bead.
5. the method that a kind of utilization organic macromolecule material according to claim 4 makees catalyst preparation ITO nano wires, its It is characterised by, from room temperature to the heating rate of annealing temperature is 100 DEG C/s during high annealing, the cooling rate after annealing is 80℃/s。
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