CN109494228A - A kind of nonvolatile memory and preparation method thereof with multidigit store function - Google Patents
A kind of nonvolatile memory and preparation method thereof with multidigit store function Download PDFInfo
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- CN109494228A CN109494228A CN201811325575.5A CN201811325575A CN109494228A CN 109494228 A CN109494228 A CN 109494228A CN 201811325575 A CN201811325575 A CN 201811325575A CN 109494228 A CN109494228 A CN 109494228A
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- H10B—ELECTRONIC MEMORY DEVICES
- H10B51/00—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory transistors
- H10B51/30—Ferroelectric RAM [FeRAM] devices comprising ferroelectric memory transistors characterised by the memory core region
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- 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]
- H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
- H10K10/474—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure
Abstract
The present invention relates to non-volatile memories fields, more particularly to a kind of nonvolatile memory with multidigit store function, nonvolatile memory provided by the invention is bottom grating structure, and the nonvolatile memory successively includes substrate, gate electrode, the ferroelectricity gate dielectric layer of three-layer composite structure, organic semiconductor layer and source-drain electrode；The ferroelectricity gate dielectric layer of the three-layer composite structure successively includes ferroelectric thin film, ultrathin insulating layer 1 and ultrathin insulating layer 2；The material of the ferroelectric thin film includes vinylidene-trifluoro-ethylene-chlorotrifluoroethylene or vinylidene-trifluoro-ethylene-vinyl chloride copolymer.The erasable voltage of nonvolatile memory provided by the invention with multidigit store function is less than 40V, and field-effect mobility is greater than 0.5cm2/Vs。
Description
Technical field
The present invention relates to non-volatile memories field more particularly to a kind of non-volatile memories with multidigit store function
Device and preparation method thereof.
Background technique
As information storage carrier --- memory occupies very important status in current information industry.It presses
Whether can be saved for a long time according to the information of storage, memory is divided into volatile and nonvolatile two major classes.According to device architecture with
And memory mechanism, there are many classification for memory.Wherein, organic transistor nonvolatile memory has single transistor structure
Storage unit, store the non-destructive reading of information, the non-volatile memories of information, flexible application, can low temperature preparation, can solution
The advantages that processing and is at low cost makes it promise to be the nonvolatile storage technologies of a new generation, while also by more next in the world
The good nonvolatile memory for being used as a new generation of more research institutions and major company.Organic transistor is non-volatile to be deposited
The fields such as reservoir stores in non-volatile information, integrated circuit, FPD and various wearable electronics have extensive
Application advantage, started one research boom in the whole world in recent years.
Organic transistor nonvolatile memory refers to that based on organic semiconductor, as active layer, preparation has organic crystalline
The memory device of body pipe structure.According to memory mechanism, organic transistor nonvolatile memory includes ferroelectric type and floating gate type two
Major class.Ferroelectric type organic transistor nonvolatile memory uses ferroelectric material as gate dielectric layer, in the erasable of opposed polarity
After voltage operation, the internal dipole arrangement of ferroelectricity gate dielectric layer changes and produces different polarized states；Also, its
Polarized state can persistently be kept after removing applied voltage, and incude different source-drain currents, correspond respectively to logical one and
" 0 " state, therefore it is provided with non-volatile information storage function.Floating gate type organic transistor nonvolatile memory uses
The gate dielectric layer of FGS floating gate structure；In the case where writing voltage operation, charge is stored in floating gate dielectric；In the case where wiping voltage operation, storage
It is discharged in the charge of floating gate dielectric；Because the amount of charge or polarity that are stored in floating gate dielectric are different, and produce different
Source-drain current corresponds respectively to logical one and " 0 " state；Charge can be stored in floating gate dielectric for a long time causes organic crystal
Pipe is provided with non-volatile information storage function.
In recent years, the report of organic transistor nonvolatile memory increases year by year.But most reports is organic
Transistor, non-volatile memory only has 1 store function, it may be assumed that only possesses logical zero state and 1 state, two storage states.
With multidigit store function (such as: 2 storage, i.e., possess logical zero 0,01,10,11 4 storage on single memory unit
State) organic transistor nonvolatile memory relevant report it is seldom.2012, C.Park of South Korea et al. used ferroelectricity
Polymer polyvinylidene fluoride-trifluoro-ethylene obtains the ferroelectric type organic transistor with multidigit store function as gate dielectric layer
Nonvolatile memory [Adv.Mater. (2012) 24,5910]；Chen Wenchang of TaiWan, China et al. is stayed using multiple polymers
Polar body is as charge-trapping dielectric [Macromol.Rapid Commun. (2014) 35,1039]；D.Kim of South Korea et al. is with two
Tie up semiconductor MoS2Nano flake is as charge-trapping dielectric [Nanoscale. (2014) 6,12315]；The C.M.Tran of Japan
Et al. using metal-lithium ion encapsulation fullerene be used as charge-trapping dielectric [Org.Electron. (2017) 45,234], divide
The floating gate type organic transistor nonvolatile memory with multidigit store function is not obtained.But these reported tools
There is the organic transistor nonvolatile memory of multidigit store function generally to need very high erasable voltage (80~200V), it is unfavorable
In its functionization.Therefore, the erasable voltage with the organic transistor nonvolatile memory of multidigit store function is significantly reduced
It is that rush can the practical prerequisite with industrialization to reasonable level.
The erasable voltage of ferroelectric type organic transistor nonvolatile memory is largely dependent upon as ferroelectricity grid
Curie's electric field of the ferroelectric material of dielectric layer.Currently, reported ferroelectric type organic transistor memory generally uses ferroelectricity
Polymer polyvinylidene fluoride-trifluoro-ethylene is resulted in as gate dielectric layer, higher Curie's electric field (up to 55 volt/microns)
Such memory needs higher erasable voltage (being greater than 50 volts), and which prevent its industrial applications.In addition, can be single to obtain
The erasable multidigit store function of one electricity, and the operating rate of memory is promoted, organic transistor nonvolatile memory must
Must have sufficiently large field-effect mobility, with obtain erasable voltage it is controllable, the clear channel current of different stage distinguished, with
And quick erasable and writing speed.But in the overwhelming majority it has been reported that ferroelectric type organic transistor nonvolatile memory in, because
The dipole of ferroelectric domain microcell by ferroelectricity gate dielectric layer acts on, and affects the transmission of channel carriers, causes field-effect
Mobility is too low.
Currently, not yet can lower erasable operating at voltages, field-effect mobility it is big with multidigit store function
Organic transistor nonvolatile memory.
Summary of the invention
The present invention provides a kind of nonvolatile memory and preparation method thereof with multidigit store function.The present invention mentions
The erasable voltage of the nonvolatile memory with multidigit store function supplied is less than 40V, and field-effect mobility is greater than 0.5cm2/
Vs。
The present invention provides a kind of nonvolatile memory with multidigit store function, the nonvolatile memory is
Bottom grating structure, the nonvolatile memory successively include substrate, gate electrode, three-layer composite structure ferroelectricity gate dielectric layer, have
Machine semiconductor layer and source-drain electrode；The ferroelectricity gate dielectric layer of the three-layer composite structure successively includes ferroelectric thin film, ultrathin insulating
Layer 1 and ultrathin insulating layer 2, the ultrathin insulating layer 2 are contacted with the organic semiconductor layer；The material of the ferroelectric thin film includes
Vinylidene-trifluoro-ethylene-chlorotrifluoroethylene or vinylidene-trifluoro-ethylene-vinyl chloride copolymer.
Preferably, the material of the ultrathin insulating layer 1 includes aluminium oxide, zirconium oxide, silica and poly- (4- vinyl benzene
Phenol) one of or it is a variety of；The material of the ultrathin insulating layer 2 includes polymethyl methacrylate, polystyrene, polyamides Asia
One of amine, polyvinyl alcohol and polyvinylpyrrolidone are a variety of.
Preferably, the ferroelectric thin film with a thickness of 100~1000nm, the thickness of the ultrathin insulating layer 1 and 2 is independently
For 1~50nm.
Preferably, the material of the substrate includes glass, silicon, polyethylene terephthalate, polymethylacrylic acid
One of formicester, polyethylene naphthalate, polyimides, polyether sulfone and paper are a variety of.
Preferably, the gate electrode and source-drain electrode material independently include tin indium oxide, silver, gold, copper, aluminium, stone
One of black alkene, carbon nanotube and poly- (3,4- ethene dioxythiophene) are a variety of.
Preferably, the organic semiconductor layer includes small molecule organic semiconductor layer or polymer organic semiconductor layer.
Preferably, the material of the small molecule organic semiconductor layer includes pentacene, CuPc, Phthalocyanine Zinc, perfluor phthalein
Bis- (triisopropylsilyl acetenyl) pentacenes of cyanines copper, carbon 60,6,13-, the bis- octyls of 2,7- [1] benzothiophene simultaneously [3,2-
B] [1] benzothiophene or 2,9- didecyl naphtho- [2,3-b:2 ', 3 '-F] thieno [3,2-b] thiophene.
Preferably, the material of the polymer organic semiconductor layer include poly- (3- hexyl thiophene -2,5- diyl), [N,
Bis- (2- octyldodecanol) naphthalene -1,4,5,8- pairs-(dicarboximide) -2,6- diyl of N'-] -5,5'- (the bis- thiophene of 2,2'-) }
Copolymer or poly- { [bis- (2- the octyldodecyl) -3,6- dioxo -2,3,5,6- nafoxidines of 2,5- are simultaneously [3,4-c] by 2,2'-
Pyrroles -1,4- diyl] Dithiophene -5,5'- diyl-alt- thieno [3,2-b] thiophene -2,5- diyl }.
Preferably, the organic semiconductor layer with a thickness of 20~100nm.
The present invention also provides the preparation methods of nonvolatile memory described in above-mentioned technical proposal, comprising the following steps:
Using the method for vapor deposition or spin coating, gate electrode, ferroelectric thin film, ultrathin insulating layer are sequentially prepared in substrate surface
1, ultrathin insulating layer 2, organic semiconductor layer and source-drain electrode, obtain nonvolatile memory.
The present invention provides a kind of nonvolatile memory with multidigit store function, the nonvolatile memory is
Bottom grating structure, the nonvolatile memory successively include substrate, gate electrode, three-layer composite structure ferroelectricity gate dielectric layer, have
Machine semiconductor layer and source-drain electrode；The ferroelectricity gate dielectric layer of the three-layer composite structure successively includes ferroelectric thin film, ultrathin insulating
Layer 1 and ultrathin insulating layer 2；The ultrathin insulating layer 2 is contacted with the organic semiconductor layer；The material of the ferroelectric thin film includes
Vinylidene-trifluoro-ethylene-chlorotrifluoroethylene or vinylidene-trifluoro-ethylene-vinyl chloride copolymer.
Nonvolatile memory provided by the invention with multidigit store function, with poly- with the ferroelectricity of low Curie's electric field
It closes object and prepares ferroelectric thin film, directly Curie's voltage needed for reduction ferroelectric thin film polarization reversal, significantly reduce the wiping of memory
Write voltage.The experimental results showed that the erasable voltage of nonvolatile memory provided by the invention is not higher than 40V, hence it is evident that lower than existing
There is the erasable voltage of 80~200V required for similar memory in technology.
In addition, ultrathin insulating layer 1 is capable of the polycrystalline surface of smooth ferroelectric thin film, improves the surface trap of ferroelectric thin film, subtract
The loss of few iron electric polarization stored charge, moreover it is possible to which the surface energy for improving ferroelectric thin film enhances the adhesion of ultrathin insulating layer 2；Together
When, ultrathin insulating layer 2 can improve ultrathin insulating layer 1 surface can, promote organic semi-conductor film morphology and micro-structure
Quality improves the interface trap between ultrathin insulating layer 2 and organic semiconductor layer, and then the field-effect for being obviously improved memory is moved
Shifting rate.The experimental results showed that the field-effect mobility of nonvolatile memory provided by the invention is greater than 0.5cm2/ Vs, hence it is evident that
0.001~the 0.1cm reported higher than most of similar memories2/ Vs for memory there is multidigit store function and promotion to deposit
Other performance parameters of reservoir lay the foundation.
In the present invention, the dielectric constant of the ultrathin insulating layer 1 and 2 is variant, and the two combines structure with ferroelectric thin film
At three layers of compound ferroelectricity gate dielectric layer when applied gate voltage changes, can change and distribute voltage on ferroelectric thin film
Numerical value makes it obtain different degrees of polarization, accumulates different charge density, the modulation different degrees of to channel current output,
And then obtain multidigit storage feature；The combination of ultrathin insulating layer 1 and ultrathin insulating layer 2 can also prevent ferroelectric thin film polarization from accumulating
The loss of tired charge, therefore it is able to ascend the functional reliability and stability of memory.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the nonvolatile memory provided by the invention with multidigit store function；
Fig. 2 is the nonvolatile memory with multidigit store function that provides of the embodiment of the present invention 1 in different gate voltages
The current-voltage transfer curve of scanning range；
Fig. 3 is the erasable circulation industrial for the nonvolatile memory with multidigit store function that the embodiment of the present invention 1 provides
Make characteristic；
Fig. 4 is that the charge storage for the nonvolatile memory with multidigit store function that the embodiment of the present invention 1 provides is protected
Hold characteristic.
Specific embodiment
The present invention provides a kind of nonvolatile memory with multidigit store function, the nonvolatile memory is
Bottom grating structure, the nonvolatile memory successively include substrate, gate electrode, three-layer composite structure ferroelectricity gate dielectric layer, have
Machine semiconductor layer and source-drain electrode；The ferroelectricity gate dielectric layer of the three-layer composite structure successively includes ferroelectric thin film, ultrathin insulating
Layer 1 and ultrathin insulating layer 2, the ultrathin insulating layer 2 are contacted with the organic semiconductor layer；The material of the ferroelectric thin film includes
Vinylidene-trifluoro-ethylene-chlorotrifluoroethylene or vinylidene-trifluoro-ethylene-vinyl chloride copolymer.
Nonvolatile memory provided by the invention preferably has 2 storage features.In the present invention, described non-volatile
As shown in Figure 1,1 be wherein substrate, 2 be gate electrode for the structure of memory, and 3 be ferroelectric thin film, and 4 for ultrathin insulating layer 1,5 be super
Thin dielectric layer 2,6 is organic semiconductor layer, and 7 be source-drain electrode.As shown in Figure 1, nonvolatile memory provided by the invention
Structure successively includes substrate, gate electrode, ferroelectric thin film, ultrathin insulating layer 1, ultrathin insulating layer 2, organic semiconductor layer and source-leakage
Electrode.
In the present invention, all substances are commercial goods.
Nonvolatile memory provided by the invention includes substrate.In the present invention, the material of the substrate preferably includes
Glass, silicon, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, polyimides,
One of polyether sulfone and paper are a variety of.
Nonvolatile memory provided by the invention includes gate electrode.In the present invention, the material of the gate electrode is preferred
Including one of tin indium oxide, silver, gold, copper, aluminium, graphene, carbon nanotube and poly- (3,4- ethene dioxythiophene) or a variety of.
In the present invention, the thickness of the gate electrode is preferably 30~100nm, further preferably 40~80nm.
Nonvolatile memory provided by the invention includes the ferroelectricity gate dielectric layer of three-layer composite structure.In the present invention,
The ferroelectricity gate dielectric layer of the three-layer composite structure successively includes ferroelectric thin film, ultrathin insulating layer 1 and ultrathin insulating layer 2, described
Ultrathin insulating layer 2 is contacted with the organic semiconductor layer.In the present invention, the material of the ferroelectric thin film includes vinylidene-
Trifluoro-ethylene-chlorotrifluoroethylene or vinylidene-trifluoro-ethylene-vinyl chloride copolymer.In the present invention, the ferroelectricity
The thickness of film is preferably 100~1000nm, further preferably 200~900nm, more preferably 400~800nm, more into one
Step is preferably 500~700nm.Ferroelectric thin film is designed as the above-mentioned substance with low Curie's electric field by the present invention, is effectively reduced
Curie's voltage needed for ferroelectric thin film polarization reversal, therefore significantly reduce the erasable voltage of memory.
In the present invention, the material of the ultrathin insulating layer 1 preferably includes aluminium oxide, zirconium oxide, silica and poly- (4- second
Alkenyl phenol) one of or it is a variety of；The material of the ultrathin insulating layer 2 preferably includes polymethyl methacrylate, polyphenyl second
One of alkene, polyimides, polyvinyl alcohol and polyvinylpyrrolidone are a variety of.In the present invention, the ultrathin insulating layer 1
With 2 thickness independently be preferably 1~50nm, further preferably 5~45nm, more preferably 10~40nm, further it is excellent
It is selected as 20~30nm.
Nonvolatile memory provided by the invention includes organic semiconductor layer.In the present invention, the organic semiconductor
Layer preferably includes small molecule organic semiconductor layer or polymer organic semiconductor layer, the material of the small molecule organic semiconductor layer
Preferably include pentacene, CuPc, Phthalocyanine Zinc, perfluor CuPc, carbon 60,6,13- bis- (triisopropylsilyl acetenyls)
The bis- octyls of pentacene, 2,7- [1] benzothiophene simultaneously [3,2-b] [1] benzothiophene or 2,9- didecyl naphtho- [2,3-b:2 ', 3 '-
F] thieno [3,2-b] thiophene.In the present invention, the structure of the perfluor CuPc is shown in formula I, and 6, the 13- is bis-, and (three is different
Propylsilyl acetenyl) pentacene structure as shown in Formula II, the bis- octyls of 2,7- [1] benzothiophene is simultaneously [3,2-b]
[1] structure of benzothiophene is as shown in formula III, 2,9- didecyl naphtho- [2,3-b:2 ', 3 '-F] thieno [3, the 2-b] thiophene
The structure of pheno is as shown in formula IV:
In the present invention, the material of the polymer organic semiconductor layer preferably includes poly- (3- hexyl thiophene -2,5- bis-
Base), { [N, N'- bis- (2- octyldodecanol) naphthalene -1,4,5,8- double-(dicarboximide) -2,6- diyl] -5,5'- (2,2'-
Double thiophene) } copolymer or poly- { 2,2'- [(bis- (2- the octyldodecyl) -3,6- dioxo -2,3,5,6- nafoxidines of 2,5-
And [3,4-c] pyrroles -1,4- diyl)] Dithiophene -5,5'- diyl-alt- thieno [3,2-b] thiophene -2,5- diyl.At this
In invention, the structure of poly- (3- hexyl thiophene -2,5- diyl) is shown as a formula V, { [bis- (the 2- octyldodecyls of N, N'-
Alcohol) naphthalene -1,4,5,8- is double-(dicarboximide) -2,6- diyl] -5,5'- (the bis- thiophene of 2,2'-) copolymer structure such as Formula IV
It is shown, poly- { 2,2'- [(2,5- bis- (2- octyldodecyl) -3,6- dioxos -2,3,5, the 6- nafoxidines simultaneously [3,4-
C] pyrroles -1,4- diyl)] Dithiophene -5,5'- diyl-alt- thieno [3,2-b] thiophene -2,5- diyl structure such as formula
Shown in VII:
In the present invention, the thickness of the organic semiconductor layer is preferably 20~100nm, further preferably 30~
90nm, more preferably 40~80nm are still more preferably 50~70nm.
Nonvolatile memory provided by the invention includes source-drain electrode.In the present invention, the material of the source-drain electrode
Matter independently preferably include tin indium oxide, silver, gold, copper, aluminium, graphene, in carbon nanotube and poly- (3,4- ethene dioxythiophene)
It is one or more.In the present invention, the thickness of the source-drain electrode is preferably 70~90nm, further preferably 75~
85nm。
The present invention also provides the preparation methods of nonvolatile memory described in above-mentioned technical proposal, comprising the following steps:
Using the method for vapor deposition and/or spin coating, gate electrode, ferroelectric thin film, ultrathin insulating layer 1, super is sequentially prepared in substrate surface
Thin dielectric layer 2, organic semiconductor layer and source-drain electrode, obtain nonvolatile memory.
In the present invention, the preparation method preferably includes following steps:
(1) gate electrode is prepared in substrate surface using vacuum heat deposition；
(2) the surface gate electrode spin coating ferroelectric polymers solution obtained in the step (1), obtains ferroelectric thin film；
(3) ultrathin insulating layer 1 is prepared on the ferroelectric thin film surface that the step (2) obtains using vacuum heat deposition；
(4) the 1 surface spin coating polymer solutions of ultrathin insulating layer obtained in the step (3), obtain ultrathin insulating layer 2；
(5) organic semiconductor layer is prepared on 2 surface of ultrathin insulating layer that the step (4) obtains using vacuum heat deposition；
(6) source-drain electrode is prepared in the organic semiconductor layer surface that the step (5) obtains using vacuum heat deposition, obtained
To nonvolatile memory.
The present invention prepares gate electrode in substrate surface using vacuum heat deposition.In the present invention, the vacuum heat deposition
Condition is preferably vacuum 8~9 × 10-4Pa, heat deposition rate are preferably 2~5 angstroms per seconds.
After substrate surface depositing gate electrode, the present invention is in surface gate electrode spin coating ferroelectric polymers solution.In the present invention
In, the mass concentration of the ferroelectric polymers solution is preferably 5%~15%, and further preferably 10%；The ferroelectric polymer
The solvent of object solution preferably includes butyl acetate.In the present invention, the condition of the spin coating be preferably spin coating rate 2000~
5000 revs/min, further preferably 3000 revs/min.The present invention passes through adjustment solution concentration and spin coating rate within the above range,
The ferroelectric film thickness that can be optimized and revised.
After the completion of spin coating, the present invention preferably heats spin-coated layer, molten in ferroelectric polymers solution to remove
Agent obtains ferroelectric thin film.In the present invention, the temperature of the heat treatment is preferably 110~130 DEG C, further preferably 120
DEG C, the time is preferably 110~130min, further preferably 120min.
After obtaining ferroelectric thin film, the present invention prepares ultrathin insulating layer 1 on ferroelectric thin film surface using vacuum heat deposition.At this
In invention, when the ultrathin insulating layer 1 is poly- (4-Vinyl phenol), spin coating proceeding is directlyed adopt in ferroelectric thin film surface system
Standby ultrathin insulating layer 1.In the present invention, the mass concentration of poly- (4-Vinyl phenol) is preferably 0.2%~1%, into one
Step preferably 0.5%；The condition of the spin coating is preferably 1000~6000 revs/min of spin coating rate, further preferably 3000 turns/
Point.The present invention can optimize and revise poly- (4-Vinyl phenol) by adjustment solution concentration and spin coating rate within the above range
The thickness of film.
In the present invention, when the ultrathin insulating layer 1 is metal oxide, the present invention first uses vacuum heat deposition in iron
Then film surface deposited metal carries out UV ozone processing, metal is oxidized to metal oxide, obtains ultrathin insulating layer
1.In the present invention, the condition of the vacuum vapor deposition is preferably vacuum 5~7 × 10-4Pa, heat deposition rate are preferably low
In 0.5 angstroms per second, further preferably 0.1~0.3 angstroms per second；The time of the UV ozone processing is preferably 25~35min, into
One step is preferably 30min.
After obtaining ultrathin insulating layer 1, the present invention obtains ultrathin insulating in 1 surface spin coating polymer solutions of ultrathin insulating layer
Layer 2.In the present invention, the mass concentration of the polymer solution is preferably 0.3%~0.8%, and further preferably 0.5%；
The solvent of the polymer solution preferably includes chlorobenzene.In the present invention, the condition of the spin coating is preferably spin coating rate 1000
~5000 revs/min, further preferably 2500 revs/min.
After the completion of spin coating, the present invention preferably heats spin-coated layer, to remove the solvent in polymer solution, obtains
To ultrathin insulating layer 2.In the present invention, the temperature of the heat treatment is preferably 110~130 DEG C, further preferably 120
DEG C, the time is preferably 10~30min, further preferably 20min.
After obtaining ultrathin insulating layer 2, the present invention prepares organic semiconductor on 2 surface of ultrathin insulating layer using vacuum heat deposition
Layer.In the present invention, the condition of the vacuum vapor deposition is preferably vacuum 1~4 × 10-4Pa, organic semi-conductor heat
Deposition rate is 0.1~0.5 angstroms per second.
After obtaining organic semiconductor layer, the present invention prepares source-electric leakage in organic semiconductor layer surface using vacuum heat deposition
Pole obtains nonvolatile memory.The present invention does not specially require the vacuum vapor deposition in source-drain electrode preparation process,
Using those skilled in the art's common method.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.
Embodiment 1:
A kind of ferroelectric type organic transistor nonvolatile memory is bottom grating structure, from top to bottom successively by substrate, grid electricity
Pole, the ferroelectricity gate dielectric layer of three-layer composite structure, organic semiconductor layer and source-drain electrode composition；The three-layer composite structure
Ferroelectricity gate dielectric layer by with low Curie's electric field ferroelectric thin film be superimposed two layers of ultra-thin insulating layer (ultrathin insulating layer 1 and 2)
Building composition.
Wherein, substrate is polyethylene naphthalate (PEN) flexible substrate, and gate electrode is aluminium, and ferroelectric thin film is inclined
Vinyl fluoride-trifluoro-ethylene-chlorotrifluoroethylene copolymer, ultrathin insulating layer 1 are aluminium oxide；Ultrathin insulating layer 2 is poly- methyl-prop
E pioic acid methyl ester；Organic semiconductor layer is pentacene, source-electric leakage extremely copper,
Gate electrode with a thickness of 40nm, ferroelectric thin film with a thickness of 700nm, ultrathin insulating layer 1 with a thickness of 4nm, it is ultra-thin
Insulating layer 2 with a thickness of 30nm, organic semiconductor layer with a thickness of 40nm, source-drain electrode is with a thickness of 70nm.
The preparation process of the nonvolatile memory is as follows:
Firstly, substrate is placed in multi-source organic molecule/vapor deposited metal system, using vacuum heat deposition technique, make
For gate electrode.
Then, ferroelectric material vinylidene-trifluoro-ethylene-chlorotrifluoroethylene is dissolved in butyl acetate solvent
In, configure solution, concentration be 10% (mass percent), after configured vinylidene-trifluoro-ethylene-chlorotrifluoroethylene is total
The solution of polymers drips on gate electrode, using spin coating proceeding, prepares one layer of vinylidene-trifluoro-ethylene-chlorotrifluoroethylene copolymerization
The ferroelectric thin film of object.Later, it will be prepared for the substrate of ferroelectric thin film, be placed in baking oven, 120 DEG C, heated 120 minutes, removal
Remaining butyl acetate solvent.
The substrate after heating is again placed in multi-source organic molecule/vapor deposited metal system again, it is heat sink using vacuum
Product technique grows one layer of ultra-thin aluminium film in ultra-thin ferroelectric film surface.Then, substrate is placed in UV ozone processing system
In, progress UV ozone processing, the time 30 minutes.So that ultra-thin aluminium film of the preparation on ferroelectric thin film surface be oxidized to it is ultra-thin
Aluminum oxide film, as ultrathin insulating layer 1.
Then, insulating material of polymer polymethyl methacrylate is dissolved in chlorobenzene solvent, configures solution, concentration is
0.5% (mass percent), after by the solution of configured polymethyl methacrylate drop ultrathin alumina film (ultra-thin absolutely
Edge layer 1) on, using spin coating proceeding, prepare one layer of polymethyl methacrylate film.Later, ultrathin insulating layer 2 will be prepared for
Substrate is placed in baking oven, 120 DEG C, is heated 20 minutes, is removed remaining chlorobenzene solvent.
Finally, the ferroelectricity gate dielectric layer of three-layer composite structure is placed in multi-source organic molecule/vapor deposited metal system
In, using vacuum heat deposition technique, on the surface of ultrathin insulating layer 2, one layer of pentacene (organic semiconductor) film is grown, is deposited
0.2 angstroms per second of rate.And then, Copper thin film is grown as source-electric leakage on the surface of pentacene using vacuum heat deposition technique
Pole.Using mask plate to source-drain electrode patterns, the channel length and width of the device of preparation are 100 microns and 1000 respectively
Micron.
Embodiment 2:
A kind of ferroelectric type organic transistor nonvolatile memory is bottom grating structure, from top to bottom successively by substrate, grid electricity
Pole, the ferroelectricity gate dielectric layer of three-layer composite structure, organic semiconductor layer and source-drain electrode composition；The three-layer composite structure
Ferroelectricity gate dielectric layer by with low Curie's electric field ferroelectric thin film be superimposed two layers of ultra-thin insulating layer (ultrathin insulating layer 1 and 2)
Building composition.
Wherein, substrate is glass, and gate electrode is tin indium oxide, and ferroelectric thin film is vinylidene-trifluoro-ethylene-trifluoro chloroethene
Alkene copolymer, ultrathin insulating layer 1 are poly- (4-Vinyl phenol)；Ultrathin insulating layer 2 is polystyrene；Organic semiconductor layer is 2,
The bis- octyls of 7- [1] benzothiophene simultaneously [3,2-b] [1] benzothiophene, source-electric leakage is extremely golden,
Gate electrode with a thickness of 100nm, ferroelectric thin film with a thickness of 800nm, ultrathin insulating layer 1 with a thickness of 30nm, surpass
Thin dielectric layer 2 with a thickness of 25nm, organic semiconductor layer with a thickness of 60nm, source-drain electrode is with a thickness of 90nm.
Embodiment 3:
A kind of ferroelectric type organic transistor nonvolatile memory is bottom grating structure, from top to bottom successively by substrate, grid electricity
Pole, the ferroelectricity gate dielectric layer of three-layer composite structure, organic semiconductor layer and source-drain electrode composition；The three-layer composite structure
Ferroelectricity gate dielectric layer by with low Curie's electric field ferroelectric thin film be superimposed two layers of ultra-thin insulating layer (ultrathin insulating layer 1 and 2)
Building composition.
Wherein, substrate is polyether sulfone, and gate electrode is silver, and ferroelectric thin film is vinylidene-trifluoro-ethylene-chloroethylene copolymer
Object, ultrathin insulating layer 1 are zirconium oxide；Ultrathin insulating layer 2 is polyvinyl alcohol；Organic semiconductor layer is CuPc, and source-electric leakage is extremely
Copper,
Gate electrode with a thickness of 30nm, ferroelectric thin film with a thickness of 850nm, ultrathin insulating layer 1 with a thickness of 5nm, it is ultra-thin
Insulating layer 2 with a thickness of 35nm, organic semiconductor layer with a thickness of 30nm, source-drain electrode is with a thickness of 85nm.
Embodiment 4:
A kind of ferroelectric type organic transistor nonvolatile memory is bottom grating structure, from top to bottom successively by substrate, grid electricity
Pole, the ferroelectricity gate dielectric layer of three-layer composite structure, organic semiconductor layer and source-drain electrode composition；The three-layer composite structure
Ferroelectricity gate dielectric layer by with low Curie's electric field ferroelectric thin film be superimposed two layers of ultra-thin insulating layer (ultrathin insulating layer 1 and 2)
Building composition.
Wherein, substrate is polyimides, and gate electrode is copper, and ferroelectric thin film is vinylidene-trifluoro-ethylene-chloroethylene copolymer
Object, ultrathin insulating layer 1 are aluminium oxide；Ultrathin insulating layer 2 is polymethyl methacrylate；Organic semiconductor layer is that { [N, N'- are bis-
- 1,4,5,8- pairs-(dicarboximide) -2,6- diyl of (2- octyldodecanol) naphthalene] -5,5'- (the bis- thiophene of 2,2'-) } copolymerization
Object, source-electric leakage is extremely silver-colored,
Gate electrode with a thickness of 45nm, ferroelectric thin film with a thickness of 550nm, ultrathin insulating layer 1 with a thickness of 3nm, it is ultra-thin
Insulating layer 2 with a thickness of 20nm, organic semiconductor layer with a thickness of 55nm, source-drain electrode is with a thickness of 75nm.
Performance test
It is deposited using ferroelectric type organic transistor of the Agilent B1500A semiconductor test analyzer to preparation is non-volatile
The electric property of reservoir is tested, and all tests are carried out in atmosphere at room temperature environment.
The nonvolatile memory that the embodiment of the present invention 1 provides turns in the current-voltage of different gate voltage scanning ranges
It is as shown in Figure 2 to move characteristic；What the nonvolatile memory that embodiment 1 provides obtained under different erasable voltage operations has multidigit
The storage cycle characteristics of (2) storage features is as shown in Figure 3；The charge storage for the nonvolatile memory that embodiment 1 provides is protected
It is as shown in Figure 4 to hold characteristic.
From Fig. 2~4 it is found that nonvolatile memory provided by the invention can obtain under different gate voltage scanning ranges
Different memory windows and storage electric current ratio；Respectively under+40, -20, -30 erasable voltage operations with -40V, 00,01 is obtained,
10 and 11 4 storage states, four storage states can be good at switching and prolonged holding, at practical 20,000 seconds
Data store in retention time test, and the 00 of expression, 01,10 there is no significantly declining with the electric currents of 11 4 storage states
Subtract.These are statistics indicate that ferroelectric type organic transistor nonvolatile memory of the invention has under lower erasable voltage
Good storage performance, and there is multidigit to store feature.With it has been reported that other organic crystals with multidigit store function
Pipe nonvolatile memory (operating voltage is generally 80~200V) is compared, and ferroelectric type organic transistor of the invention is non-volatile
Memory obtains good multidigit (2) store function in the case where lower voltage is erasable；In addition, being calculated by Fig. 2, this Shen
Please embodiment 1 provide nonvolatile memory field-effect mobility > 0.5cm2Thus/Vs illustrates provided by the present application non-
Volatile memory field-effect mobility is higher.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of nonvolatile memory with multidigit store function, the nonvolatile memory is bottom grating structure, described
Nonvolatile memory successively include substrate, gate electrode, the ferroelectricity gate dielectric layer of three-layer composite structure, organic semiconductor layer and
Source-drain electrode；The ferroelectricity gate dielectric layer of the three-layer composite structure successively include ferroelectric thin film, ultrathin insulating layer 1 and it is ultra-thin absolutely
Edge layer 2, the ultrathin insulating layer 2 are contacted with the organic semiconductor layer；The material of the ferroelectric thin film includes vinylidene-three
Vinyl fluoride-chlorotrifluoroethylene or vinylidene-trifluoro-ethylene-vinyl chloride copolymer.
2. nonvolatile memory according to claim 1, which is characterized in that the material of the ultrathin insulating layer 1 includes
One of aluminium oxide, zirconium oxide, silica and poly- (4-Vinyl phenol) are a variety of；The material packet of the ultrathin insulating layer 2
Include one of polymethyl methacrylate, polystyrene, polyimides, polyvinyl alcohol and polyvinylpyrrolidone or a variety of.
3. nonvolatile memory according to claim 1 or 2, which is characterized in that the ferroelectric thin film with a thickness of 100
The thickness of~1000nm, the ultrathin insulating layer 1 and 2 independently are 1~50nm.
4. nonvolatile memory according to claim 1, which is characterized in that the material of the substrate include glass,
Silicon, polyethylene terephthalate, polymethyl methacrylate, polyethylene naphthalate, polyimides, polyether sulfone
With one of paper or a variety of.
5. nonvolatile memory according to claim 1, which is characterized in that the gate electrode and source-drain electrode
Material independently include tin indium oxide, silver, gold, copper, aluminium, graphene, in carbon nanotube and poly- (3,4- ethene dioxythiophene)
It is one or more.
6. nonvolatile memory according to claim 1, which is characterized in that the organic semiconductor layer includes small point
Sub- organic semiconductor layer or polymer organic semiconductor layer.
7. nonvolatile memory according to claim 6, which is characterized in that the small molecule organic semiconductor layer
Material includes pentacene, CuPc, Phthalocyanine Zinc, perfluor CuPc, carbon 60,6,13- bis- (triisopropylsilyl acetenyls)
The bis- octyls of pentacene, 2,7- [1] benzothiophene simultaneously [3,2-b] [1] benzothiophene or 2,9- didecyl naphtho- [2,3-b:2 ', 3 '-
F] thieno [3,2-b] thiophene.
8. nonvolatile memory according to claim 6, which is characterized in that the polymer organic semiconductor layer
Material includes poly- (3- hexyl thiophene -2,5- diyl), { [bis- (2- octyldodecanol) naphthalene -1,4,5,8- pairs-(diformazan of N, N ' -
Acid imide) -2,6- diyl] -5,5 '-(2,2 '-bis- thiophene) } copolymer or poly- { 2,2'- [(bis- (the 2- octyldodecyls of 2,5-
Base) -3,6- dioxo -2,3,5,6- nafoxidine simultaneously [3,4-c] pyrroles -1,4- diyl)] Dithiophene -5,5'- diyl-alt-
Thieno [3,2-b] thiophene -2,5- diyl }.
9. according to the described in any item nonvolatile memories of claim 6~8, which is characterized in that the organic semiconductor layer
With a thickness of 20~100nm.
10. the preparation method of any one of claim 1~9 nonvolatile memory, comprising the following steps:
Using the method for vapor deposition and/or spin coating, gate electrode, ferroelectric thin film, ultrathin insulating layer are sequentially prepared in substrate surface
1, ultrathin insulating layer 2, organic semiconductor layer and source-drain electrode, obtain nonvolatile memory.
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| US20040002176A1 (en) * | 2002-06-28 | 2004-01-01 | Xerox Corporation | Organic ferroelectric memory cells |
| CN106531887A (en) * | 2016-12-05 | 2017-03-22 | 吉林大学 | Low-temperature erasable ferroelectric organic transistor nonvolatile memory |
| CN107275483A (en) * | 2017-04-25 | 2017-10-20 | 南京大学 | It is a kind of based on the fast ferroelectric transistorized memory of two-dimentional organic molecular semiconductors and preparation |
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| US20040002176A1 (en) * | 2002-06-28 | 2004-01-01 | Xerox Corporation | Organic ferroelectric memory cells |
| CN106531887A (en) * | 2016-12-05 | 2017-03-22 | 吉林大学 | Low-temperature erasable ferroelectric organic transistor nonvolatile memory |
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| CN110047996A (en) * | 2019-04-24 | 2019-07-23 | 南京大学 | Super low-power consumption ferroelectric crystal cast memory based on two-dimentional organic functional material and preparation method thereof |
| CN110047996B (en) * | 2019-04-24 | 2021-01-05 | 南京大学 | Ultra-low power consumption ferroelectric transistor type memory based on two-dimensional organic functional material and preparation method thereof |
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