CN109256467A - High-performance single wall carbon nano-tube film transistor and preparation method thereof - Google Patents
High-performance single wall carbon nano-tube film transistor and preparation method thereof Download PDFInfo
- Publication number
- CN109256467A CN109256467A CN201811044695.8A CN201811044695A CN109256467A CN 109256467 A CN109256467 A CN 109256467A CN 201811044695 A CN201811044695 A CN 201811044695A CN 109256467 A CN109256467 A CN 109256467A
- Authority
- CN
- China
- Prior art keywords
- plasma
- carbon nano
- film transistor
- tube
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/221—Carbon nanotubes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/464—Lateral top-gate IGFETs comprising only a single gate
-
- 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
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
- H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
-
- 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
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Present invention discloses a kind of preparation methods of high-performance single wall carbon nano-tube film transistor, the process of the contact area of metal electrode and semiconductor layer is prepared in this method, including the evenly dispersed semi-conductor type single-walled carbon nano tube for having been subjected to separating-purifying in organic solvent to be placed on substrate and dry, carbon pipe film is prepared；Depositing electrode region is treated to pattern obtained using plasma and carries out local etching processing, by adjusting the gas flow in plasma treatment procedure, power, etch period occur for plasma, to control the local etching to carbon pipe film；On the carbon pipe film of above-mentioned local etching, source-drain electrode of the deposit metal electrodes as thin film transistor (TFT).The present invention is suitable for technical grade batch preparation high-purity semi-conductor type single-walled carbon nano tube material, can prepare High-performance micro-nano rice device and complicated integrated circuit using this kind of semiconductor material.
Description
Technical field
The invention belongs to carbon nanotube technology field more particularly to a kind of high-performance single wall carbon nano-tube film transistor and
Preparation method.
Background technique
Semi-conductor type single-walled carbon nano tube (s-SWNT) is given more sustained attention with its unique structure and characteristic electron, is relied on
Its small size, high mobility and flexible structure are sent to great expectations and are applied to field effect transistor, infrared acquisition, Flexible Displays, penetrate
The function elements such as frequency and integrated circuit.
In recent years, the s-SWNT based on solwution method separation achieves extraordinary progress, and isolated semiconductor purity
Reach 99.9% or more, it is very fast using upper progress in micron devices, and achieve extraordinary achievement.
But the s-SWNT institute that the mobility of device and current density are directly grown relative to chemical vapour deposition technique (CVD)
Preparing device still has certain gap；And the smaller and smaller s-SWNT for making traditional CVD growth of channel dimensions of micro-nano device
In the case that purity is not able to satisfy application demand, the high-purity s-SWNT equally separated to solwution method brings challenges.
When device channel is reduced to hundreds of nanometers of scales or less, most of carbon nanotube can be directly connected to source and drain electricity
Pole, because carrier scattering caused by carbon pipe overlap joint largely reduces in channel.At this point, connecing between carbon pipe and metal electrode
Electric shock resistance is to influence the important factor in order of device electric property, and the interface state of carbon pipe and electrode directly affects the note of carrier
Enter efficiency.On the one hand, the dispersing agent impurity introduced in solwution method preparation process, which is deposited on carbon pipe surface, can bring quenching for carrier
It goes out and scatters.On the other hand, electrode, the film of multilayer carbon pipe composition either are prepared with top contact mode or the bottom way of contact
There is also many problems for coming into full contact between metal electrode.Current existing document report is by changing carbon pipe and electrode
The way of contact improves contact resistance using the methods of the matched metal electrode material of work content or change device architecture, but is difficult
The above both sides is solved the problems, such as, to realize the Ohmic contact between carbon pipe and electrode.
Summary of the invention
One of the objects of the present invention is to provide a kind of quickly controllable and the existing semiconducter process of compatibility preparation is high
The method of performance single wall carbon nano-tube film transistor.
Another object of the present invention is to provide the high-performance single wall carbon nano-tube film being in the above way prepared is brilliant
Body pipe.
It is brilliant another object of the present invention is to provide the high-performance single wall carbon nano-tube film being in the above way prepared
Body pipe is come the method that constructs micro/nano level device and circuit.
For achieving the above object, on the one hand, the present invention provides a kind of high-performance single wall carbon nano-tube film crystal
The preparation method of pipe prepares the process of the contact area of metal electrode and semiconductor layer in this method, comprising the following steps:
S1, the evenly dispersed semi-conductor type single-walled carbon nano tube for having been subjected to separating-purifying in organic solvent is placed in lining
Carbon pipe film is prepared on bottom；
S2, the carbon pipe film described in S1 carry out photoetching process or graphical printing technology, obtain electrode zone to be deposited
Pattern；
S3, accurate etching processing is carried out using plasma apparatus electrode zone to be deposited described in S2, passes through adjusting
Power, etch period occur for gas flow, plasma in plasma treatment procedure, to control the part to carbon pipe film
Etching；
S4, the local etching described in S3 carbon pipe film on, source-drain electrode of the deposit metal electrodes as thin film transistor (TFT).
As the further improvement of embodiment of the present invention, which further includes preparation and the gate electrode of insulating layer
Preparation process, and insulating layer and gate electrode are constructed according to bottom grating structure or top gate structure, form complete thin film transistor (TFT).
As the further improvement of embodiment of the present invention, before step S1, this method further includes passing through organic conjugate
Purity partly leading greater than 99% is prepared in Selective Separation process between molecule or conjugated polymer and single-walled carbon nanotube
The organic solution of figure single-walled carbon nanotube.
As the further improvement of embodiment of the present invention, prepared in the S1 carbon pipe film mode include dip coating,
Spray coating method, cast coating method, czochralski method, trans-printing or contact printing method.
It is specific to the local etching of carbon pipe film in the step S3 as the further improvement of embodiment of the present invention
For to the local etching of carbon pipe film specifically, etching condition is controlled by accurate, by the carbon pipe of contact zone in the step S3
Carbon tube layer number etching in film is single layer or the single layer for remaining local carbon pipe.
As the further improvement of embodiment of the present invention, the step S3 plasma etches the plasma used
Generator includes RF excitaton source, inductively-coupled plasma sources or Transformer Coupled Plasma source；
It is 50-500W that power, which occurs, for the plasma that the step S3 plasma etching uses.
As the further improvement of embodiment of the present invention, the step S3 plasma gaseous species include oxygen,
Any one or any several mixing of argon gas and hydrogen-nitrogen gaseous mixture.
As the further improvement of embodiment of the present invention, the step S3 plasma gas flow is 50-
500sccm/s。
As the further improvement of embodiment of the present invention, the etch period of the step S3 plasma etching is
10-45s。
As the further improvement of embodiment of the present invention, the etch period of the step S3 plasma etching is
150-600s。
On the other hand, the present invention also provides the high-performance carbon nanotube film crystals that should be prepared with the aforedescribed process
Pipe.
In another aspect, the present invention also provides a kind of above-mentioned high-performance carbon nanotube thin film transistor (TFT)s of application to construct micro-nano
The method of meter level device and circuit, specifically includes the following steps:
Uniform film is formed on the substrate in the attachment of semi-conductor type single-walled carbon nano tube material；
Micro/nano level patterning and surface and interface processing are carried out to the film；
Using the patterned film as the semiconductor portions of micro/nano level electronic device.
The present invention provides a kind of quickly controllable and compatible semiconducter process preparation high-performance single wall carbon nano-tube film
The method of transistor, has the advantages that
Compared with prior art, present invention discloses one kind to prepare network-like carbon pipe thin film transistor (TFT) (CNT-TFT) mistake
Plasma etch process is introduced in Cheng Zhong, carbon pipe and the processing of metal electrode contact interface to improve the side of contact resistance influence
Method.First by optimization ultrasound and centrifugal condition, the s-SWNT solution of high-purity, low defect is obtained, and in the preparation of CNT-TFT
Plasma etching industrial is introduced in technique, carbon pipe film and electrode contact region is handled, to adjust contact circle of carbon pipe and electrode
Face and contact condition.Average contact resistance can be reduced to original 1/5th by the etching condition after optimization, be eventually formed
Contact resistance can be reduced to 3.3K Ω by the edge termination way of contact；The hole mobility of CNT-TFT is improved to nearly 100cm2V-
1s-1 reaches the level of polysilicon.A kind of method that the present invention has developed quickly controllable and compatible conventional semiconductors processing technology,
It has very important significance to the single wall carbon nano-tube film transistor preparation of micro-nano size channel.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Exemplary embodiment and its explanation please is not constituted an undue limitation on the present application for explaining the application；Wherein:
Fig. 1 is the absorption spectrum of the carbon nano-tube solution after the separation in the embodiment of the present invention 1；
Fig. 2 is the Raman spectrum of carbon nano-tube solution after separating in the embodiment of the present invention 1；
Fig. 3 a be CNT-TFT on-state current and off-state current with the different etching time variation diagram；
Fig. 3 b is the hole carrier mobility of CNT-TFT with the variation diagram of different etching time；
Fig. 3 c is the linear transfer characteristic curve of CNT-TFT corresponding to untreated, plasma etching 20s and 300s
Figure；
Fig. 3 d is the transfer characteristic curve figure of the CNT-TFT after optimization；
Fig. 4 is isolated length of carbon nanotube statistical chart；
Fig. 5 is different etching time corresponding carbon pipe film morphology figure；
Fig. 6 is the Raman spectrum variation diagram of the carbon pipe film of different etching time；
Fig. 7 a Y is the 2Rc figure of the CNT-TFT for the different etching time-triggered protocol that function calculates；
Fig. 7 b is variation diagram of the average contact resistance with etch period；
Fig. 7 c-7f is the contact interface of carbon pipe and electrode with the variation diagram of etch period.
Specific embodiment
To keep the purposes, technical schemes and advantages of the application clearer, below in conjunction with the application specific embodiment
And technical scheme is clearly and completely described in corresponding attached drawing.Obviously, described embodiment is only this Shen
Please a part of embodiment, rather than whole embodiment.Based on the embodiment in the application, ordinary skill people
Member's every other embodiment obtained without making creative work, shall fall in the protection scope of this application.
Embodiments of the present invention are described below in detail, the example of the embodiment is shown in the accompanying drawings, wherein from beginning
Same or similar element or element with the same or similar functions are indicated to same or similar label eventually.Below by ginseng
The embodiment for examining attached drawing description is exemplary, and for explaining only the invention, and is not considered as limiting the invention.
For achieving the above object, the present invention provides a kind of preparations of high-performance single wall carbon nano-tube film transistor
Method prepares the universal process of the contact area of metal electrode and semiconductor layer in this method, comprising the following steps:
It is prepared by the Selective Separation process between organic conjugated molecule or conjugated polymer and single-walled carbon nanotube pure
The organic solution of semi-conductor type single-walled carbon nano tube of the degree greater than 99%；
The evenly dispersed semi-conductor type single-walled carbon nano tube for having been subjected to separating-purifying in organic solvent is placed in substrate
On prepare carbon pipe film；
Specifically, the mode that carbon pipe film is prepared in S1 includes dip coating, spray coating method, cast coating method, czochralski method, transfer
Printing or contact printing method.
The carbon pipe film carries out photoetching process or graphical printing technology, obtains the pattern of electrode zone to be deposited；
Accurate etching processing is carried out to the electrode zone to be deposited using plasma apparatus, by adjusting plasma
Power, etch period occur for gas flow, plasma in treatment process, to control the local etching to carbon pipe film；
On the carbon pipe film of the local etching, source-drain electrode of the deposit metal electrodes as thin film transistor (TFT).
Specifically, the local etching to carbon pipe film is specifically, control etching condition by accurate, by the carbon pipe of contact zone
Carbon tube layer number etching in film is single layer or the single layer for remaining local carbon pipe.
Optionally, the plasma generator that plasma etching uses includes RF excitaton source, inductively coupled plasma body
Source or Transformer Coupled Plasma source；
Preferably, it is 50-500W that power, which occurs, for the plasma that plasma etching uses.
Optionally, plasma gas type include oxygen, argon gas and hydrogen-nitrogen gaseous mixture any one or it is any
Several mixing.
Wherein, plasma gas flow amount is 50-500sccm/s.
As the further improvement of embodiment of the present invention, the etch period of plasma etching is 10-45s；On or
Stating etch period is 150-600s.
As the further improvement of embodiment of the present invention, which further includes preparation and the gate electrode of insulating layer
Preparation process, and insulating layer and gate electrode are constructed according to bottom grating structure or top gate structure, form complete thin film transistor (TFT).
Illustrate the preparation process of high-performance single wall carbon nano-tube film transistor with concrete example below,
Embodiment 1
Firstly, preparing semi-conductor type single-walled carbon nano tube；
In embodiment disclosed by the invention, used single-walled carbon nanotube is the single-wall carbon tube of arc catalyzing method preparation
(Carbon Solution company of the U.S., the entitled AP-SWCNTs of product, the average diameter of carbon pipe are 1.4nm) or Hipco type list
Wall carbon pipe (NanoIntegris company of the U.S., lot number P2-771, carbon pipe diameter are distributed 0.8-1.2nm).
The preferred polymers of this experiment separating-purifying s-SWNTs are that linear polymer polycarbazole derivative PCz (is purchased from Suzhou
Xi Yin nanosecond science and technology Co., Ltd), opposed helical type canoe is weaker with the interaction force of carbon pipe, therefore can lead to
The method of filtering cleaning and redisperse further purifies isolated carbon pipe.
PCz polymer and Arc carbon nanotube are accurately weighed for 2:1 in mass ratio, it is preferable that accurately weigh PCz polymer
10mg and ARC carbon pipe 50mg is blended in 20 milliliters of toluene solvants, and water bath sonicator 5min is uniformly mixed；
Ultrasonic disperse 30min is carried out using Probe Ultrasonic Searching wave crusher, circulator bath temperature is controlled at 20 DEG C；
Carbon pipe solution after dispersion is subjected to high speed centrifugation, the supernatant obtained after centrifugation is the dispersion of preliminary purification
Semiconductor type carbon nano-tube (s-SWNTs).
In the specific implementation of present disclosure, the main process selectively dispersed is exactly ultrasound and centrifugation；Pass through ultrasound
The pencil carbon pipe of initial growth is opened, carbon pipe is opened post-consumer polymer Molecular Adsorption to carbon pipe surface, and passes through centrifugation selection
The isolated semiconductor type carbon nano-tube of property.
As the further improvement of embodiment of the present invention, after the s-SWNTs solution for obtaining PCz separation, aperture is selected
Vacuum filter is carried out for 0.1 μm of teflon membrane filter, the s-SWNTs solid separated at this time is stayed on filter membrane, then utilized
THF solvent repeatedly rinses the s-SWNTs powder of filter membrane surface.
Still further, obtained s-SWNTs solid powder can have the organic solvent compared with highly dissoluble to carbon pipe
In pass through simple water bath sonicator realize redisperse, preferably selection chloroform dispersion cleaning after s-SWNTs.
Filtrate obtained in experimentation can be recycled, and can recycle polymer and solvent again after revolving,
The cost of separation process can be greatly lowered by recycling polymer and organic solvent.
The characterization of purity and pattern is carried out to the above-mentioned s-SWNT being prepared；
As shown in Figure 1, the Φ value that can obtain characterization s-SWNT solution semiconductor purity by testing absorption spectrum is increased to
0.443, illustrate that isolated s-SWNT semiconductor purity reaches 99.99%；
And according to Raman Spectrometer point counting from the G/D ratio of carbon pipe characterize the effect of separation；As shown in Figure 2, lead to
The G/D ratio for crossing the isolated carbon pipe of above-mentioned experiment condition is 33；It is using the s-SWNT average length that AFM counts separation
1.8 μm, the s-SWNTs length obtained higher than other reported solwution methods.As it can be seen that being obtained by above-mentioned optimization separation condition
The s-SWNTs solution of high-purity, low defect.
Further, using above-mentioned obtained s-SWNTs solution, high-performance carbon nanotube thin film transistor (TFT) is prepared；
Specific preparation method the following steps are included:
S1, it will drip on substrate and dry by ultrasound and the evenly dispersed carbon nanotube in organic solvent of centrifugation, make
Standby carbon pipe film；
Preferably, the method for preparing carbon pipe film is dip coating；Concrete operation step are as follows:
The Si/SiO2 substrate for pre-processing clean is put into carbon nano-tube film depositing in carbon nano-tube solution；
Post-depositional substrate is taken out with being dried with nitrogen, dries 30min on 120 DEG C of warm tables, is i.e. completion carbon nano-tube network
The preparation of network shape film.
By changing the concentration of carbon nano-tube solution and the density of the adjustable carbon nano-tube film of sedimentation time.This implementation
The sedimentation time for the carbon nano-tube film that example uses is 2h.
In other embodiments, specifically, the preparation of carbon pipe film is also an option that following methods:
Czochralski method, spray coating method, cast coating method, inkjet printing, trans-printing or contact printing method, these methods more than
Based on stating the clean stable dispersions obtained after filtering cleaning, optimization allotment appropriate is carried out to realize the preparation or print of film
Brush.
S2, photoetching treatment is carried out to carbon pipe film, process, obtains the pattern of electrode zone to be deposited through exposure and development；Tool
Body, drying back substrate is placed on yellow light area spin coating photoresist and carries out first time photoetching, transistor is prepared by photoetching process
Source-drain electrode pattern.
After S3, development, processing is performed etching to above-mentioned electrode zone to be deposited using plasma, passes through adjusting etc.
Power, etch period occur for gas flow, plasma in gas ions treatment process, realize and carve to the part of carbon pipe film
Erosion is etched the carbon pipe film number of plies of contact zone for single layer or partial mono-layer by controlling etching condition.
Specifically, in thin film transistor (TFT) preparation process, plasma etching used in embodiment disclosed by the invention is set
Standby type is ICP-RIE equipment, after exposure electrode pattern development, utilizes the electrode pattern region of plasma etching exposure；
It is 100W that power, which occurs, for the plasma used, and plasma gas type is oxygen, oxygen flow 100sccm/s, control
Other conditions are identical, and setting etch period is respectively 10s, 20s, 30s, 45s, 60s, 90s and 300s.
The etch period of the preferably described step S3 plasma etching is 10-45s；Or etch period is 150-
600s。
On the carbon pipe film of above-mentioned local etching, source-drain electrode of the deposit metal electrodes as thin film transistor (TFT).
S4, the preparation method further include the preparation of insulating layer and the preparation process of gate electrode, and insulating layer and gate electrode are pressed
It is constructed according to bottom grating structure or top gate structure, forms complete thin film transistor (TFT).
Specifically, the present embodiment uses heavily-doped Si as gate electrode, and silicon dioxide layer is as insulating layer.Pass through second of photoetching
Channel region is defined, and removes the carbon pipe outside thin film transistor channel with plasma etching, realizes carbon nano-tube film transistor
Preparation.
And can also include following methods for the surface modification of base silica:
A) OTS is modified
It takes 5mL OTS to the edge of glass culture dish, dry SiO2 piece is placed on to the intermediate region of culture dish, culture dish
It is placed in vacuum drying oven, vaporization temperature is heated to 60 DEG C, keeps 30min.
B) alkylation modification
The sample that will be modified be placed on vacuum drying oven be heated to 130 DEG C vacuumize after, to sample surfaces spray hexamethyl two
Silicon amine (CH3) 3SiNHSi (CH3) 3 steam, the process are mainly completed in HMDS pretreatment system.
C) hydrophilicity-imparting treatment
The sample modified will be needed to be placed in 4mL plasma degumming machine, 100W power, oxygen flow 100scan/s are set
Reaction time 2min.
The performance and carbon pipe film morphology of the carbon nano-tube film transistor of S5, characterization after plasma etching treatment；
It is specific further comprising the steps of:
S501, with the variation of carbon pipe film in Raman Characterization plasma etch process；
S502, the different etching time is characterized to the shadow of carbon pipe film morphology with atomic force microscope and scanning electron microscope
It rings；
The performance of S503, the thin film transistor (TFT) prepared with semiconductor parametric tester test.
The on-state current and off-state current that Fig. 3 a is CNT-TFT, can be with from Fig. 3 a with the variation diagram of different etching time
It was found that the variation of certain rule is presented with etch period in the on-state current of CNT-TFT, and it is able to maintain OFF state and is basically unchanged；And
There is peak value when etch period is 20s and 300s, on-state current by it is untreated when 130 μ A be increased to 240 μ A.
Fig. 3 b is to prepare the hole mobility of device with the variation diagram of etch period, and mobility is mentioned from 56cm2V-1s-1
Height arrives 91cm2V-1s-1, reaches the higher level based on network-like thin film transistor (TFT) reported at present.
Fig. 3 c is the linear transfer characteristic curve of the untreated corresponding CNT-TFT of plasma etching 20s and 300s, right
Than discovery, plasma etching threshold voltage while improving current density is introduced in the contact interface of carbon pipe and electrode and is also sent out
Given birth to offset, this is mainly due to etching process introduce oxygen atom and caused by.
Fig. 3 d is the typical logarithm transfer characteristic curve of CNT-TFT after optimization, channel length and width be respectively 2 μm and
10μm.Due to being to test transfer characteristic curve under air conditions, CNT-TFT shows as p-type carrier transport.
Further, the film morphology of CNT-TFT is characterized；
For the changing rule that front CNT-TFT electric current occurs, the state of film under the conditions of different etching is refined
Research；Testing the different etching time first corresponds to the AFM shape appearance figure of film, as shown in figure 5, the carbon pipe thin-film network not handled
There are many bright spots in network lap-joint, illustrates to remain impurity on film, may include a small amount of residual photoresist and the polymerization of carbon pipe surface
Object.The etching that can be seen that low-power from the AFM figure of etching 10s and 20s makes carbon pipe film surface become clean.Work as etch period
It when extending to 30s and 45s, observes that s-SWNTs film is thinned out from AFM figure, also occurs being broken on corresponding SEM figure bad
s-SWNTs.When but the time further extends to 60s, sparse s-SWNTs can also be scanned on AFM figure at this time, but at this time
Substantially there is no s-SWNTs on SEM figure, the degree for illustrating that carbon pipe electronic structure at this time is destroyed is very big.When to 90s, AFM figure is aobvious
What is shown is discontinuous several, and corresponding SEM has been scanned less than s-SWNTs, and carbon pipe interconnects when illustrating to etch into 90s
Network is seriously damaged, and cannot form conductive network structure.When etch period extends to 300s, film is complete
Full etching is left the hydroxylated surface SiO2.
The Raman spectrum variation diagram of the carbon pipe film of Fig. 6 different etching time, further characterizes the mistake by Raman spectrum
The variation of journey s-SWNTs.It is 0s to 20s by etch period is one group of comparison to better describe, 30s to 90s is other one
Group.Fig. 6 a is the untreated, Raman spectrogram that measures under 633nm laser of etching 10s and 20s, it can be seen that etch period
When for 10s and 20s, the peak G of s-SWNTs reduces general, the peak defect D enhancing；Illustrate low-power short time corona treatment not
It is only capable of the remaining photoresist impurity of clean surface, a small amount of defect can be also introduced in carbon pipe surface, sp2 hydridization in part becomes in carbon pipe
At sp3 hydridization.
Fig. 6 b is the Raman spectrum comparison diagram of etch period carbon pipe film from 30s to 90s.It was found that when etch period is 45s,
The G peak intensity of s-SWNTs is attenuated to suitable with defect D peak intensity.When etch period extends to 90s, the characteristic peak base of s-SWNTs
This disappearance cannot reach the Monitoring lower-cut of Raman, illustrate that film is largely destroyed, what this was also characterized with front
AFM figure is corresponding.
On this basis, by the contact resistance of Y functional simulation calculating carbon pipe and electrode with the variation of etching, Fig. 7 a is
The carbon pipe and interelectrode contact resistance (2Rc) calculated using Y function, Fig. 7 b is variation of the average contact resistance with etch period
Figure, 2Rc by it is untreated when 14.46K Ω drop to plasma etching 300s when 3.36K Ω.
Fig. 7 c-7f shows model analysis different etching period carbon pipe and interelectrode interface conditions according to building.
When being first untreated, carbon pipe surface has a small amount of remaining photoresist and polymer after photoetching development, influences the injection of carrier
Contact of the efficiency with high quality；After the processing of low-power short time, carbon pipe and electrode contact interface gradually become clean, and carbon pipe
Film surface part sp2 hydridization becomes sp3 hydridization and contacts with electrode more abundant, improves Carrier Injection Efficiency；When etching
Between when further extending, carbon managed network is destructurized serious at this time, and damaged carbon pipe consumes certain charge；It will finally carve
The erosion time extends to 300, and electrode pattern region carbon pipe is etched completely away, and forms positive T-type photoetching agent pattern, photoresist end
After etching still can exposed portion carbon pipe, plate top electrode after, just can with the end of the carbon pipe of exposing formed edge termination contact,
This way of contact can realize the contact of high quality, thus the current density highest of film CNT-TFT.
Embodiment 2
The present invention further discloses the high-performance single-walled carbon nanotube that method described in Application Example 1 is prepared
Thin film transistor (TFT).
Embodiment 3
The high-performance single wall carbon nano-tube film transistor building provided the present invention also provides Application Example 2 is micro-nano
The method of grade device and circuit, specifically includes the following steps:
Uniform film is formed on the substrate in the attachment of semi-conductor type single-walled carbon nano tube material；
Micro/nano level patterning and surface and interface processing are carried out to the film；
Using the patterned film as the semiconductor portions of micro/nano level electronic device.
The present invention provides a kind of quickly controllable and compatible semiconducter process preparation high-performance single wall carbon nano-tube film
The method of transistor, has the advantages that
Compared with prior art, present invention discloses one kind to prepare network-like carbon pipe thin film transistor (TFT) (CNT-TFT) mistake
Plasma etch process is introduced in Cheng Zhong, carbon pipe and the processing of metal electrode contact interface to improve the side of contact resistance influence
Method.First by optimization ultrasound and centrifugal condition, the s-SWNT solution of high-purity, low defect is obtained, and in the preparation of CNT-TFT
Plasma etching industrial is introduced in technique, carbon pipe film and electrode contact region is handled, to adjust contact circle of carbon pipe and electrode
Face and contact condition.Average contact resistance can be reduced to original 1/5th by the etching condition after optimization, be eventually formed
Contact resistance can be reduced to 3.3K Ω by the edge termination way of contact；The hole mobility of CNT-TFT is improved to nearly 100cm2V-
1s-1 reaches the level of polysilicon.A kind of method that the present invention has developed quickly controllable and compatible conventional semiconductors processing technology,
It has very important significance to the single wall carbon nano-tube film transistor preparation of micro-nano size channel.
It should be appreciated that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should will say
As a whole, the technical solution in each embodiment may also be suitably combined to form those skilled in the art can for bright book
With the other embodiments of understanding.
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically
Protection scope that is bright, being not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention or change
More it should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high-performance single wall carbon nano-tube film transistor, which is characterized in that prepare metal in this method
The process of the contact area of electrode and semiconductor layer, comprising the following steps:
S1, the evenly dispersed semi-conductor type single-walled carbon nano tube for having been subjected to separating-purifying in organic solvent is placed on substrate
Prepare carbon pipe film；
S2, the carbon pipe film described in S1 carry out photoetching process or graphical printing technology, obtain the figure of electrode zone to be deposited
Case；
S3, carry out accurate etching processing using plasma apparatus electrode zone to be deposited described in S2, by adjust etc. from
Power, etch period occur for gas flow, plasma in daughter treatment process, to control the part quarter to carbon pipe film
Erosion；
S4, the local etching described in S3 carbon pipe film on, source-drain electrode of the deposit metal electrodes as thin film transistor (TFT).
2. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that should
Preparation method further includes preparing insulating layer and preparing the process of gate electrode, and insulating layer and gate electrode are according to bottom grating structure or top-gated
Structure is constructed, and complete thin film transistor (TFT) is formed.
3. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that
Before step S1, this method further includes by the selectivity between organic conjugated molecule or conjugated polymer and single-walled carbon nanotube
The organic solution of semi-conductor type single-walled carbon nano tube of the purity greater than 99% is prepared in separation process.
4. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that institute
Stating and preparing the mode of carbon pipe film in S1 includes dip coating, spray coating method, cast coating method, czochralski method, trans-printing or contact print
Brush method.
5. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that institute
It states in step S3 to the local etching of carbon pipe film specifically, etching condition is controlled by accurate, by the carbon pipe film of contact zone
In carbon tube layer number etching be single layer or the single layer for remaining local carbon pipe.
6. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that institute
Stating the plasma generator that step S3 plasma etching uses includes RF excitaton source, inductively-coupled plasma sources or change
Depressor coupling plasma source；
It is 50-500W that power, which occurs, for the plasma；
The step S3 plasma gaseous species include any one of oxygen, argon gas and hydrogen-nitrogen gaseous mixture or appoint
It anticipates several mixing；
The step S3 plasma gas flow is 50-500sccm/s.
7. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that institute
The etch period for stating step S3 plasma etching is 10-45s.
8. the preparation method of high-performance single wall carbon nano-tube film transistor according to claim 1, which is characterized in that institute
The etch period for stating step S3 plasma etching is 150-600s.
9. brilliant using the high-performance single wall carbon nano-tube film that method according to any one of claims 1 to 8 is prepared
Body pipe.
10. application high-performance single wall carbon nano-tube film transistor according to claim 9 building micro/nano level device with
The method of circuit, which comprises the following steps:
Uniform film is formed on the substrate in the attachment of semi-conductor type single-walled carbon nano tube material；
Micro/nano level patterning and surface and interface processing are carried out to the film；
Using the patterned film as the semiconductor portions of micro/nano level electronic device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811044695.8A CN109256467B (en) | 2018-09-07 | 2018-09-07 | High-performance single-walled carbon nanotube thin film transistor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811044695.8A CN109256467B (en) | 2018-09-07 | 2018-09-07 | High-performance single-walled carbon nanotube thin film transistor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109256467A true CN109256467A (en) | 2019-01-22 |
| CN109256467B CN109256467B (en) | 2022-08-26 |
Family
ID=65048001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811044695.8A Active CN109256467B (en) | 2018-09-07 | 2018-09-07 | High-performance single-walled carbon nanotube thin film transistor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109256467B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993793A (en) * | 2019-12-06 | 2020-04-10 | 中国科学院空间应用工程与技术中心 | Method for preparing semi-conductive carbon nano tube quasi-array film |
| CN111129205A (en) * | 2019-12-06 | 2020-05-08 | 国家纳米科学中心 | Carbon nano tube-Z907 composite thin film photoelectric transistor and preparation method and application thereof |
| CN111370578A (en) * | 2020-03-20 | 2020-07-03 | 中国科学院微电子研究所 | Bionic transistor structure and control method of characteristic time thereof |
| CN113557212A (en) * | 2019-03-08 | 2021-10-26 | 东丽株式会社 | Carbon nanotube composition, semiconductor element, and wireless communication device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540285A (en) * | 2009-04-16 | 2009-09-23 | 上海交通大学 | Method for preparing carbon nano tube thin-film field-effect transistor |
| CN101667611A (en) * | 2009-09-15 | 2010-03-10 | 上海交通大学 | Preparation method of solar micro battery on basis of directional carbon nano tube |
| CN102530854A (en) * | 2012-01-17 | 2012-07-04 | 上海交通大学 | Method for preparing semiconductor single-walled carbon nanotube by adopting a room-temperature plasma etching method |
| US20120202347A1 (en) * | 2011-02-07 | 2012-08-09 | Georgia Tech Research Corporation | Through silicon vias using carbon nanotubes |
| US20140124783A1 (en) * | 2012-06-08 | 2014-05-08 | Panasonic Corporation | Thin-film transistor and method for manufacturing thin-film transistor |
| CN108163840A (en) * | 2017-12-27 | 2018-06-15 | 深圳市华星光电半导体显示技术有限公司 | Carbon nanotube method of purification, thin film transistor (TFT) and preparation method |
-
2018
- 2018-09-07 CN CN201811044695.8A patent/CN109256467B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101540285A (en) * | 2009-04-16 | 2009-09-23 | 上海交通大学 | Method for preparing carbon nano tube thin-film field-effect transistor |
| CN101667611A (en) * | 2009-09-15 | 2010-03-10 | 上海交通大学 | Preparation method of solar micro battery on basis of directional carbon nano tube |
| US20120202347A1 (en) * | 2011-02-07 | 2012-08-09 | Georgia Tech Research Corporation | Through silicon vias using carbon nanotubes |
| CN102530854A (en) * | 2012-01-17 | 2012-07-04 | 上海交通大学 | Method for preparing semiconductor single-walled carbon nanotube by adopting a room-temperature plasma etching method |
| US20140124783A1 (en) * | 2012-06-08 | 2014-05-08 | Panasonic Corporation | Thin-film transistor and method for manufacturing thin-film transistor |
| CN108163840A (en) * | 2017-12-27 | 2018-06-15 | 深圳市华星光电半导体显示技术有限公司 | Carbon nanotube method of purification, thin film transistor (TFT) and preparation method |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113557212A (en) * | 2019-03-08 | 2021-10-26 | 东丽株式会社 | Carbon nanotube composition, semiconductor element, and wireless communication device |
| CN113557212B (en) * | 2019-03-08 | 2023-12-22 | 东丽株式会社 | Carbon nanotube composition, semiconductor element, and wireless communication device |
| CN110993793A (en) * | 2019-12-06 | 2020-04-10 | 中国科学院空间应用工程与技术中心 | Method for preparing semi-conductive carbon nano tube quasi-array film |
| CN111129205A (en) * | 2019-12-06 | 2020-05-08 | 国家纳米科学中心 | Carbon nano tube-Z907 composite thin film photoelectric transistor and preparation method and application thereof |
| CN111129205B (en) * | 2019-12-06 | 2021-10-08 | 国家纳米科学中心 | Carbon nano tube-Z907 composite thin film photoelectric transistor and preparation method and application thereof |
| CN111370578A (en) * | 2020-03-20 | 2020-07-03 | 中国科学院微电子研究所 | Bionic transistor structure and control method of characteristic time thereof |
| CN111370578B (en) * | 2020-03-20 | 2022-08-30 | 中国科学院微电子研究所 | Bionic transistor structure and control method of characteristic time thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109256467B (en) | 2022-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109256467A (en) | High-performance single wall carbon nano-tube film transistor and preparation method thereof | |
| Zhang et al. | Growth of semiconducting single-wall carbon nanotubes with a narrow band-gap distribution | |
| Lefebvre et al. | High-purity semiconducting single-walled carbon nanotubes: a key enabling material in emerging electronics | |
| DE19711268B4 (en) | Chemical vapor deposition process with inductively coupled plasma, use of the process for the production of thin film transistors and thin films made of amorphous silicon by the process | |
| Tulevski et al. | Toward high-performance digital logic technology with carbon nanotubes | |
| Jordan et al. | Synthesis of graphene nanoribbons via the topochemical polymerization and subsequent aromatization of a diacetylene precursor | |
| US11069867B2 (en) | Electronically pure single chirality semiconducting single-walled carbon nanotube for large scale electronic devices | |
| CN105819425B (en) | A kind of high-purity semiconductor type carbon nano-tube and its lot splitting method and application | |
| CN105611986B (en) | Method for purifying semiconductor single-walled carbon | |
| CN101730917B (en) | Transparent electroconductive thin film and process for producing the transparent electroconductive thin film | |
| Li et al. | Surface effects on network formation of conjugated polymer wrapped semiconducting single walled carbon nanotubes and thin film transistor performance | |
| Yu et al. | Recycling strategy for fabricating low-cost and high-performance carbon nanotube TFT devices | |
| Wu et al. | Self‐Assembly of Semiconducting Single‐Walled Carbon Nanotubes into Dense, Aligned Rafts | |
| Tyagi et al. | Ultra-clean high-mobility graphene on technologically relevant substrates | |
| CN103337362A (en) | Nano capacitor and preparation method thereof | |
| CN103466612A (en) | Method for preparing native grapheme by means of frequency mixing ultrasound | |
| Mesgari et al. | Gel electrophoresis using a selective radical for the separation of single-walled carbon nanotubes | |
| Liu et al. | High-yield and low-cost separation of high-purity semiconducting single-walled carbon nanotubes with closed-loop recycling of raw materials and solvents | |
| Reis et al. | Highly efficient and scalable separation of semiconducting carbon nanotubes via weak field centrifugation | |
| CN106478927B (en) | Carbon nanotube-non-linear conjugated polymer, preparation method and application | |
| KR20190131598A (en) | Array Substrate, Method of Manufacturing Display Substrate and Display Panel | |
| Vijayaraghavan | Bottom‐up assembly of nano‐carbon devices by dielectrophoresis | |
| CN110358309B (en) | Silica gel/carbon nano tube dielectric elastomer composite material and preparation method thereof | |
| Jain et al. | Effect of source, surfactant, and deposition process on electronic properties of nanotube arrays | |
| KR20160131454A (en) | Method for preparation of graphene by using dye |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190211 Address after: 215000 No. 1368 Wuzhong Avenue, Wuzhong Economic Development Zone, Suzhou City, Jiangsu Province Applicant after: SUZHOU XIYIN NANO TECHNOLOGY Co.,Ltd. Address before: 215131 No. 160 Sun Road, Huangqiao Street, Xiangcheng District, Suzhou City, Jiangsu Province Applicant before: SUZHOU XINTI NANO TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |