CN110429032A - One kind being based on Ni3(HITP)2The preparation method of the field effect transistor of conductive MOF film - Google Patents
One kind being based on Ni3(HITP)2The preparation method of the field effect transistor of conductive MOF film Download PDFInfo
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- CN110429032A CN110429032A CN201910700639.3A CN201910700639A CN110429032A CN 110429032 A CN110429032 A CN 110429032A CN 201910700639 A CN201910700639 A CN 201910700639A CN 110429032 A CN110429032 A CN 110429032A
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- 239000010408 film Substances 0.000 title claims abstract description 62
- 230000005669 field effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000013299 conductive metal organic framework Substances 0.000 title claims abstract description 26
- 239000013300 Ni 3(2,3,6,7,10,11-hexaiminotriphenylene)2 Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 238000011065 in-situ storage Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 24
- 239000010703 silicon Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- -1 amino trimethylene benzole Chemical compound 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 15
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000002262 irrigation Effects 0.000 description 5
- 238000003973 irrigation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012923 MOF film Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- PUXBEKLSMBVFNW-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexamine hexahydrochloride Chemical compound Cl.Cl.Cl.Cl.Cl.Cl.NC1=CC=2C3=CC(=C(C=C3C3=CC(=C(C=C3C2C=C1N)N)N)N)N PUXBEKLSMBVFNW-UHFFFAOYSA-N 0.000 description 2
- 208000035541 Device inversion Diseases 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
Abstract
The invention belongs to field effect transistor fields, are based on Ni more particularly, to one kind3(HITP)2The preparation method of the field effect transistor of conductive MOF film.Transistor device comprising three end of source and drain grid and channel is placed in Ni3(HITP)2In reaction solution, so that obtaining Ni by solid-liquid interface method growth in situ at the channel of the transistor device3(HITP)2Film is obtained based on Ni3(HITP)2The field effect transistor of conductive MOF film.Thus solve the prior art based on Ni3(HITP)2The technical issues of insecure in conjunction with substrate existing for the preparation method of the field effect transistor of conductive MOF film, field effect transistor caused by poor contact is good, uniformity is poor etc. carrier transmission performance and sensitive poor performance.
Description
Technical field
The invention belongs to field effect transistor fields, are based on Ni more particularly, to one kind3(HITP)2Conductive MOF film
Field effect transistor preparation method.
Background technique
New Two Dimensional MOF material Ni3(HITP)2Property and graphene it is closely similar, but compared to graphene its with band
The advantages that gap characteristic, and reaction condition is mild, synthesis is simple, has high surface area 630m2/ g, high conductivity (its conductance
Rate σ is about 5000S/m, is more than active carbon and porous graphite), Ni-N abundant4Active site.Therefore there are these peculiar properties
Ni3(HITP)2It can be used as the excellent selection of the active channel material of field effect transistor.
Preparation is based on Ni3(HITP)2The critical issue of the field effect transistor of conductive MOF film is how to turn MOF film
It moves on at the channel of FET, common method has drop-coating, spin-coating method, punching press transfer method etc., such as by Ni3(HITP)2Powder is matched
Dispersion liquid is made and carries out drop coating or spin coating in silicon chip surface, or directly shifts Ni with substrate3(HITP)2Film, but these methods
Can have the shortcomings that in conjunction with substrate it is insecure, poor contact is good, uniformity is poor etc., therefore will affect the load of field effect transistor
Flow sub- transmission performance and sensitive performance.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides one kind to be based on Ni3(HITP)2Conductive MOF
The preparation method of the field effect transistor of film, by the way that the transistor device comprising three end of source and drain grid and channel is placed in Ni3
(HITP)2In reaction solution, so that obtaining Ni by solid-liquid interface method growth in situ at the channel of the transistor device3
(HITP)2Film is obtained based on Ni3(HITP)2The field effect transistor of conductive MOF film, thus solve the prior art based on
Ni3(HITP)2Insecure in conjunction with substrate, poor contact existing for the preparation method of the field effect transistor of conductive MOF film
The technical problem of good, uniformity difference etc..
To achieve the above object, according to one aspect of the present invention, it provides a kind of based on Ni3(HITP)2Conductive MOF is thin
The preparation method of the field effect transistor of film, which is characterized in that be placed in the transistor device comprising three end of source and drain grid and channel
Ni3(HITP)2In reaction solution, so that being obtained at the channel of the transistor device by solid-liquid interface method growth in situ
Ni3(HITP)2Film is obtained based on Ni3(HITP)2The field effect transistor of conductive MOF film.
Preferably, the transistor device comprising three end of source and drain grid and channel obtains by the following method: in titanium dioxide
Mask ultraviolet photolithographic, magnetron sputtering depositing electrode and organic solvent is passed sequentially through in silicon/silicon base to remove photoresist to obtain.
It preferably, will include that the transistor device at three end of source and drain grid and channel is placed in Ni3(HITP)2Before reaction solution,
It further comprises the steps of: and handles the transistor device in ozone environment, by ozone treatment to increase the device surface hydroxyl
The quantity of base.
Preferably, the Ni3(HITP)2Reaction solution be by the six water nickel chloride solutions of 0.5~2.5mg/mL, 0.3~
Six amino trimethylene benzole soln of 1.65mg/mL and alkaline reagent are according to volume ratio 50:50:(3~35) it is mixed to get；The alkalinity
Reagent is ammonium hydroxide or hydrazine hydrate.
Preferably, the Ni3(HITP)2Reaction solution obtains by the following method: by the six water chlorine of 0.5~2.5mg/mL
After change nickel solution is mixed with ammonium hydroxide, under stirring condition, the solution of 0.3~1.65mg/mL, six amino trimethylene benzole soln is added dropwise
In.
Preferably, face-down by comprising the transistor device at three end of source and drain grid and channel one with channel, it is suspended in institute
State Ni3(HITP)2Reaction solution surface, so that growth in situ obtains Ni at the channel of the transistor device3(HITP)2It is thin
Film.
Preferably, the transistor device comprising three end of source and drain grid and channel is placed in Ni3(HITP)2In reaction solution, 40
At~70 DEG C, reaction 5~180 minutes are stood, so that growth in situ obtains Ni at the channel of the transistor device3(HITP)2
Film.
Preferably, the preparation method further comprises the steps of: the Ni for obtaining growth in situ3(HITP)2Film is successively adopted
It is cleaned with ethyl alcohol and deionized water, it is then 2~12 hours dry at 60~100 DEG C.
Preferably, the transistor device comprising three end of source and drain grid and channel is placed in Ni3(HITP)2In reaction solution, and institute
It states other places of the transistor device in addition to channel to cover using exposure mask, throws off the exposure mask after reaction to growth in situ,
So that only growth in situ obtains Ni at the channel of the transistor device3(HITP)2Film.
In general, in order to overcome Ni3(HITP)2Conductive MOF film is transferred to the problem on field effect transistor, this
Invention provides a kind of based on solid-liquid interface method growth in situ acquisition Ni3(HITP)2The system of conductive MOF thin film transistor
Preparation Method, the development for MOF base field-effect transistor provide new approaches.Through the invention contemplated above technical scheme with
The prior art is compared, and can achieve the following beneficial effects:
(1) the present invention provides one kind to be based on Ni3(HITP)2The preparation method of the field effect transistor of conductive MOF film,
It is by being placed in Ni for the transistor device comprising three end of source and drain grid and channel3(HITP)2In reaction solution, so that in the crystalline substance
Ni is obtained by solid-liquid interface method growth in situ at the channel of body tube device3(HITP)2Film is obtained based on Ni3(HITP)2It leads
The field effect transistor of electric MOF film.This method is due to Ni3(HITP)2Reaction solution passes through solid liquid interface on channel material surface
Growth in situ is obtained based on Ni3(HITP)2Conductive MOF structural membrane, and the film is firmly combined at channel with substrate,
Contact is good, uniformity is good, and the carrier transmission performance for the field effect transistor being accordingly manufactured to and sensitive performance also have larger
The raising of degree.
(2) Ni provided by the invention3(HITP)2The preparation method of conductive MOF thin film transistor is first using ultraviolet
Photoetching, magnetron sputtering depositing electrode, the acetone technologies such as remove photoresist prepare basic FET device substrate, then by device
Inversion is suspended in Ni3(HITP)2Reaction solution in, growth in situ obtains large stretch of complete, thick at the channel of scene effect transistor
Spend uniform Ni3(HITP)2Film carries out electric performance test.
(3) present invention has good field effect behavior, and can regulate and control Ni by the control reaction time3(HITP)2It is thin
Film and be based on Ni3(HITP)2The performance of thin film transistor.
Detailed description of the invention
Fig. 1 is Ni produced by the present invention3(HITP)2FET device figure；
Fig. 2 (a) is Ni obtained in the embodiment of the present invention 13(HITP)2Scanning electricity at the channel of field effect transistor
Mirror figure；Fig. 2 (b) is Ni obtained in embodiment 13(HITP)2The scanning electron microscope (SEM) photograph of film；Fig. 2 (c) is made in embodiment 1
The Ni obtained3(HITP)2The scanning electron microscope (SEM) photograph of the cross section of film (reaction 30min)；Fig. 2 (d) is Ni obtained in embodiment 23
(HITP)2The scanning electron microscope (SEM) photograph of the cross section of film (reaction 15min).
Fig. 3 (a) is Ni obtained in the embodiment of the present invention 13(HITP)2The X-ray photoelectron of film (reaction 30min)
Energy spectrum diagram；Fig. 3 (b) is Ni obtained in embodiment 23(HITP)2The x-ray photoelectron spectroscopy figure of film (reaction 15min).
Fig. 4 (a) is Ni obtained in the embodiment of the present invention 13(HITP)2The output characteristic curve of film (reaction 30min)
Figure；Fig. 4 (b) is Ni obtained in embodiment 13(HITP)2The output characteristic curve figure of film (reaction 15min)；Fig. 4 (c) is
Obtained Ni in embodiment 23(HITP)2The transfer characteristic curve figure of film (reaction 30min)；Fig. 4 (d) is institute in embodiment 2
Ni obtained3(HITP)2The transfer characteristic curve figure of film (reaction 15min).
Fig. 5 is Ni obtained in the embodiment of the present invention 13(HITP)2The transfer characteristic curve point of film (reaction 30min)
Analysis figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides one kind to be based on Ni3(HITP)2The preparation method of the field effect transistor of conductive MOF film, will wrap
The transistor device of three end of grid containing source and drain and channel is placed in Ni3(HITP)2In reaction solution, so that in the transistor device
Ni is obtained by solid-liquid interface method growth in situ at channel3(HITP)2Film is obtained based on Ni3(HITP)2Conductive MOF film
Field effect transistor.
In some embodiments, the transistor device comprising three end of source and drain grid and channel obtains by the following method: In
It removes photoresist to obtain by being successively masked ultraviolet photolithographic, magnetron sputtering deposition titanium/gold electrode, acetone in silica/silicon substrate.
The silica/silicon substrate refers to using silicon as substrate there is the silica with a thickness of 280~300nm in silicon substrate surface
Silicon wafer.
In some embodiments, the transistor device comprising three end of source and drain grid and channel obtains by the following method: choosing
The silicon wafer for being 280~300nm with silicon dioxide thickness impregnates ultrasound with acetone, ethyl alcohol and deionized water respectively.In silicon chip surface
Spin coating BP212-37S photoresist, front baking carry out ultraviolet photolithographic, development by mask, dry after carrying out after being dried with nitrogen.Using magnetic control
It sputters in silicon wafer substrate and is sequentially depositing titanium layer and gold electrode layer, the channel length between source and drain is 50 μm, width 2000
μm.Ultrasound is finally impregnated in acetone, rinses clean device surface with ethyl alcohol, water.
It is some to be in embodiment, it will include that the transistor device at three end of source and drain grid and channel is placed in Ni3(HITP)2Reaction
It before solution, further comprises the steps of: and handles the transistor device in ozone environment, for example carried out in UV ozone instrument
Processing increases the quantity of hydroxyl in silicon chip surface by ozone treatment to enhance to generation based on Ni3(HITP)2Conductive MOF is thin
The suction-operated of film.Oxygen is resolved into ozone under ultraviolet light by UV ozone instrument, and ozone can aoxidize substrate, on the one hand
Some organic impurities on silicon wafer can be removed, in addition can also make to generate hydroxyl on silicon wafer.
Ni of the present invention3(HITP)2At the channel of transistor device on the one hand growth film forming is because of Ni3(HITP)2Itself
Property, due between HITP ligand and the coordination and adjacent stacked layers of Ni metal center π-π interaction, Ni3
(HITP)22D structure by being self-assembly of；It on the other hand is the different surfaces energy because of solid-liquid interface, at ozone
The quantity in silicon chip surface increase hydroxyl is managed to enhance the suction-operated to the MOF material of generation, is furthermore schemed in advance on silicon wafer
The gold electrode of case activity with higher, can promote Ni during the reaction3(HITP)2Growth so that Ni3(HITP)2
It is gradually stacked on silicon wafer and forms one layer of MOF film.
In some embodiments, the photoresist of spin coating is with a thickness of 1~2 μm；The condition of front baking be 100 DEG C (hot plate), 2~
3min；The condition dried afterwards is 120 DEG C of (hot plate), 2~3min；Titanium layer is with a thickness of 5~10nm, and layer gold is with a thickness of 80~100nm；It goes
30~60s of acetone ultrasound when glue.
In some embodiments, the Ni3(HITP)2Reaction solution be by the six water nickel chloride solutions of 0.5~2.5mg/mL,
0.3~1.65mg/mL, six amino trimethylene benzole soln and alkaline reagent are according to volume ratio 50:50:(3~35) it is mixed to get；Institute
Stating alkaline reagent is ammonium hydroxide or hydrazine hydrate.
In some embodiments, in order to preferably control the MOF structure and morphology of formation, by the six water chlorine of 0.5~2.5mg/mL
After change nickel solution is mixed with ammonium hydroxide, under stirring condition, the solution of 0.3~1.65mg/mL, six amino trimethylene benzole soln is added dropwise
In, obtain the Ni3(HITP)2Reaction solution.The wherein six water nickel chloride solution, six amino trimethylene benzole solns and ammonium hydroxide
Volume ratio is 50:50:(3~35).
It is face-down by comprising the transistor device at three end of source and drain grid and channel one with channel in some embodiments, it hangs
Float on the Ni3(HITP)2Reaction solution surface, so that growth in situ obtains Ni at the channel of the transistor device3
(HITP)2Film.
In some embodiments, the transistor device comprising three end of source and drain grid and channel is placed in Ni3(HITP)2Reaction solution
In, at 40~70 DEG C, reaction 5~180 minutes are stood, so that growth in situ obtains at the channel of the transistor device
Ni3(HITP)2Film.
In some embodiments, the Ni for obtaining growth in situ is further comprised the steps of:3(HITP)2Film successively uses ethyl alcohol and goes
Ionized water is cleaned, then 2~12 hours dry at 35~100 DEG C.
In some embodiments, six water nickel chlorides, six amino trimethylene benzene are dissolved in deionized water respectively, make six water nickel chlorides
Concentration be 0.5~2.5mg/mL, the concentration of six amino trimethylene benzene is 0.3~1.65mg/mL.Under stiring to nickel chloride solution
In the ammonium hydroxide of 0.3~0.35mL is slowly added dropwise, the mixed liquor of nickel chloride and ammonium hydroxide is slowly added dropwise into six amino after being sufficiently stirred
In the benzole soln of Sanya stir 5~10min, with tweezers by transistor device obtained have electrode one down, be suspended in solution
Surface is subsequently placed in 5~180min of reaction in 40~70 DEG C of water-baths.Stop heating after reaction, is taken out after being cooled to room temperature
Field effect transistor is placed in vacuum drying oven at 35~100 DEG C dry 2 with ethyl alcohol, the multiple irrigation instrument surface of deionized water
~12h.
In some embodiments, the transistor device comprising three end of source and drain grid and channel is placed in Ni3(HITP)2Reaction solution
In, and other places of the transistor device in addition to channel are covered using exposure mask, are thrown off after reaction to growth in situ
The exposure mask, so that only growth in situ obtains Ni at the channel of the transistor device3(HITP)2Film.
In some embodiments of the invention, it is based on growth in situ Ni3(HITP)2The inspection of the field effect transistor of conductive MOF film
Survey method, detecting step are as follows:
(1) excess stock around MOF FET device top electrode prepared by the present invention is crossed out with diamond pen,
And crossing out device surface far from the silica of the pocket at electrode reveals following silicon layer, as grid electricity
Pole contact.
(2) it is combined using 4200-SCS semiconductor analysis instrument and three end probe stations, test MOF FET device
Transfer characteristic curve and output characteristic curve.
The following are embodiments:
Embodiment 1
The preparation method of field effect transistor, specific as follows:
Step A: selecting silicon dioxide thickness is the silicon wafer of 280~300nm, uses acetone, ethyl alcohol and deionization water logging respectively
Bubble ultrasound.In silicon chip surface spin coating BP212-37S photoresist, front baking, ultraviolet photolithographic, development are carried out by mask, after being dried with nitrogen
It is dried after progress.5~10nm titanium layer and 80~100nm gold electrode layer, source, leakage are sequentially depositing in silicon wafer substrate using magnetron sputtering
Channel length between end is 50 μm, width is 2000 μm.30~60s of ultrasound is finally impregnated in acetone, is rinsed with ethyl alcohol, water
Clean device surface finally obtains device as shown in Figure 1.
Step B: six water nickel chlorides, six amino trimethylene benzene are dissolved in deionized water respectively, make the concentration of six water nickel chlorides
Concentration for 2mg/mL, six amino trimethylene benzene is 1.32mg/mL, is slowly added dropwise 0.3mL's into nickel chloride solution under stiring
Ammonium hydroxide, after being sufficiently stirred by the mixed liquor of nickel chloride and ammonium hydroxide be slowly added dropwise in six amino trimethylene benzole solns stirring 5~
10min, with tweezers by field effect transistor obtained in step A have electrode one down, be suspended in solution surface, then set
30min is reacted in 65 DEG C of water-baths.After reaction stop heating, take out field effect transistor after being cooled to room temperature, with ethyl alcohol,
The multiple irrigation instrument surface of deionized water is placed in vacuum drying oven at 35 DEG C dry 6h.
Pattern is as shown in Fig. 2 (a) scanning electron microscope (SEM) photograph at the device channel being prepared: visible Ni3(HITP)2Material growth
Channel between two gold electrodes, and the structure and morphology of electrode still remains intact, and is not destroyed during the reaction；
Ni3(HITP)2Film morphology is as shown in Fig. 2 (b): being shown in growth in situ in silicon wafer substrate and obtains Ni3(HITP)2It is by layer by layer
Laminated structure is accumulated；Shown in cross-sectional morphology such as Fig. 2 (c): obtained Ni3(HITP)2The thickness of film is about 263nm；
Shown in x-ray photoelectron spectroscopy figure such as Fig. 3 (a): obtaining from Ni3(HITP)2With the C atom of water guest molecule
(284.80eV), N atom (534.04eV), the formant of O atom (534.04eV) and Ni atom (855.66eV), it was demonstrated that the original
Ni can be prepared in position growth method3(HITP)2。
Embodiment 2
With embodiment 1, difference is other steps:
Step B ': six water nickel chlorides, six amino trimethylene benzene are dissolved in deionized water respectively, make the concentration of six water nickel chlorides
Concentration for 2mg/mL, six amino trimethylene benzene is 1.32mg/mL.It is slowly added dropwise 0.3mL's into nickel chloride solution under stiring
Ammonium hydroxide, after being sufficiently stirred by the mixed liquor of nickel chloride and ammonium hydroxide be slowly added dropwise in six amino trimethylene benzole solns stirring 5~
10min, with tweezers by field effect transistor obtained in step A have electrode one down, be suspended in solution surface, then set
15min is reacted in 65 DEG C of water-baths.After reaction stop heating, take out field effect transistor after being cooled to room temperature, with ethyl alcohol,
The multiple irrigation instrument surface of deionized water is placed in vacuum drying oven at 35 DEG C dry 6h.The cross section for the device being prepared
Shown in pattern such as Fig. 2 (d), shown in x-ray photoelectron spectroscopy figure such as Fig. 3 (b), it can be seen that the shortening in reaction time can change
Become Ni3(HITP)2The thickness (about 213nm) of film, but since Ni ion and HATP ligand within a short period of time cannot be sufficiently anti-
It answers, the Ni content being integrated on HATP ligand is caused to reduce.
It is obtained above to be based on Ni3(HITP)2The test method of the field effect transistor of conductive MOF film, specific steps are such as
Under:
(1) excess stock around MOF FET device top electrode is crossed out with diamond pen, and by device surface
Silica far from the zonule at electrode, which is crossed out, reveals following silicon layer, as gate electrode contact.
(2) it is combined using 4200-SCS semiconductor analysis instrument and three end probe stations, test MOF FET device
Electrical property.
(3) in output characteristic curve Ids-VdsTest in, be arranged grid voltage Vgs10V is changed to from -10V with the step-length of 5V,
Drain-source voltage VdsTest scope in 0~2V, test result is as schemed；In transfer characteristic curve Ids-VgsTest in, setting leakage
Source voltage is fixed as -1V, grid voltage VgsTest scope in 40V~-40V.
(4) Ni being prepared in embodiment 13(HITP)2The output characteristic curve of field effect transistor such as Fig. 4 (a) institute
Show: showing that field effect transistor obtained can be by changing grid voltage Vgs(preferable tune is played from -10V to 10V) to output electric current
Control effect, shown in transfer characteristic curve such as Fig. 4 (b): showing the ambipolar performance of similar graphene-based field effect transistor；
Further to study Ni3(HITP)2The performance of field effect transistor, transfer characteristic curve analysis chart are as shown in Figure 5: passing through meter
Calculation obtains Ni3(HITP)2The current on/off ratio of field effect transistor is Ion/Ioff=1.72 × 102, carrier mobility μ=
31.63cm2/ V.s has preferable field effect behavior.
(5) Ni being prepared in embodiment 23(HITP)2The output characteristic curve of field effect transistor such as Fig. 4 (c) institute
Show: output electric current IdsNevertheless suffer from grid voltage VgsRegulating and controlling effect, but it is overall compared with the electric current in Fig. 4 (a) all declined,
This is because the reaction time, which shortens, leads to Ni3(HITP)2The consistency of film declines, and is also dropped to the transfer ability of carrier
It is low；Shown in its transfer characteristic curve such as Fig. 4 (d): field effect transistor still shows ambipolar performance.
Embodiment 3
Six water nickel chlorides, six amino trimethylene benzene are dissolved in deionized water respectively, make the concentration 2mg/ of six water nickel chlorides
ML, six amino trimethylene benzene concentration be 1.32mg/mL, the ammonium hydroxide of 0.35mL is slowly added dropwise into nickel chloride solution under stiring,
5~10min of stirring in six amino trimethylene benzole solns is slowly added dropwise in the mixed liquor of nickel chloride and ammonium hydroxide after being sufficiently stirred, uses tweezer
Son by field effect transistor obtained in 1 step A of embodiment have electrode one down, be suspended in solution surface, be subsequently placed in
60min is reacted in 65 DEG C of water-baths.Stop heating after reaction, takes out field effect transistor after being cooled to room temperature, with ethyl alcohol, go
The multiple irrigation instrument surface of ionized water is placed in vacuum drying oven at 100 DEG C dry 2h, Ni is prepared3(HITP)2Field-effect
Transistor.
Embodiment 4
Six water nickel chlorides, six amino trimethylene benzene are dissolved in deionized water respectively, make the concentration of six water nickel chlorides
2.3mg/mL, six amino trimethylene benzene concentration be 1.5mg/mL, the ammonia of 0.3mL is slowly added dropwise into nickel chloride solution under stiring
After being sufficiently stirred 5~10min of stirring in six amino trimethylene benzole solns is slowly added dropwise in the mixed liquor of nickel chloride and ammonium hydroxide by water,
With tweezers by field effect transistor obtained in 1 step A of embodiment have electrode one down, be suspended in solution surface, then
It is placed in 65 DEG C of water-baths and reacts 120min.Stop heating after reaction, takes out field effect transistor after being cooled to room temperature, use second
The multiple irrigation instrument surface of alcohol, deionized water is placed in vacuum drying oven at 100 DEG C dry 2h.Ni is prepared3(HITP)2
Effect transistor.
Ni of the method provided by the present invention based on growth in situ3(HITP)2The system of the field effect transistor of conductive MOF film
Preparation Method at least has the advantages that
(1) provided by the invention to be based on Ni3(HITP)2Field effect transistor preparation method in, it is first heavy in substrate surface
Product electrode, then pass through solid-liquid interface method growth in situ Ni3(HITP)2Film shows that this method does not destroy device by Fig. 2 (a)
Electrode pattern, and the complete MOF film of sheet being made of nanometer sheet is generated at channel.
(2) provided by the invention to be based on Ni3(HITP)2Field effect transistor preparation method in, by control react when
Length can regulate and control Ni3(HITP)2The performance of the performance of film even field effect transistor.When by Fig. 2 (c), (d) display reaction
The long thickness for influencing MOF；Fig. 3 (a), (b) display reaction duration influence Ni3(HITP)2Ni ion participates in containing for coordination in film
Amount；Fig. 3 (a), (b), (c), (d) display reaction duration influence to be based on Ni3(HITP)2The electrical property of the field effect transistor of film.
(3) provided by the invention to be based on Ni3(HITP)2Field effect transistor have good field effect behavior, pass through tune
Control grid voltage VgsPlay regulation drain-source current IdsEffect；Its threshold voltage VthFor 33.5V；Carrier mobility μ is
31.63cm2/ V.s, current on/off ratio Ion/IoffIt is 1.72 × 102。
(4) provided by the present invention to be based on Ni3(HITP)2Field effect transistor, preparation method is simple and convenient, performance
Well.
To sum up, the embodiment of the present invention has good field effect behavior, and can be by controlling reaction time tune
Control Ni3(HITP)2And it is based on Ni3(HITP)2The performance of the field effect transistor of conductive MOF film.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. one kind is based on Ni3(HITP)2The preparation method of the field effect transistor of conductive MOF film, which is characterized in that will include
The transistor device of three end of source and drain grid and channel is placed in Ni3(HITP)2In reaction solution, so that in the ditch of the transistor device
Ni is obtained by solid-liquid interface method growth in situ at road3(HITP)2Film is obtained based on Ni3(HITP)2Conductive MOF film
Field effect transistor.
2. preparation method as described in claim 1, which is characterized in that the transistors comprising source and drain grid three ends and channel
Part obtains by the following method: passed sequentially through in silica/silicon substrate mask ultraviolet photolithographic, magnetron sputtering depositing electrode and
Organic solvent removes photoresist to obtain.
3. preparation method as described in claim 1, which is characterized in that will include the transistors at source and drain grid three ends and channel
Part is placed in Ni3(HITP)2It before reaction solution, further comprises the steps of: and handles the transistor device in ozone environment, lead to
Ozone treatment is crossed to increase the quantity of the device surface hydroxyl.
4. preparation method as described in claim 1, which is characterized in that the Ni3(HITP)2Reaction solution be by 0.5~
Six water nickel chloride solutions, 0.3~1.65mg/mL, six amino trimethylene benzole soln and the alkaline reagent of 2.5mg/mL is according to volume ratio
50:50:(3~35) it is mixed to get；The alkaline reagent is ammonium hydroxide or hydrazine hydrate.
5. preparation method as claimed in claim 4, which is characterized in that the Ni3(HITP)2Reaction solution is by the following method
It obtains: after the six water nickel chloride solutions of 0.5~2.5mg/mL are mixed with ammonium hydroxide, under stirring condition, it is added dropwise 0.3~
In the solution of six amino trimethylene benzole soln of 1.65mg/mL.
6. preparation method as described in claim 1, which is characterized in that by the transistor device comprising source and drain grid three ends and channel
One with channel is face-down, is suspended in the Ni3(HITP)2Reaction solution surface, so that in the channel of the transistor device
Place's growth in situ obtains Ni3(HITP)2Film.
7. preparation method as claimed in claim 6, which is characterized in that by the transistor device comprising source and drain grid three ends and channel
It is placed in Ni3(HITP)2In reaction solution, at 40~70 DEG C, reaction 5~180 minutes are stood, so that in the transistor device
Channel at growth in situ obtain Ni3(HITP)2Film.
8. preparation method as described in claim 1, which is characterized in that further comprise the steps of: the Ni for obtaining growth in situ3
(HITP)2Film successively uses ethyl alcohol and deionized water to be cleaned, then 2~12 hours dry at 60~100 DEG C.
9. preparation method as described in claim 1, which is characterized in that by the transistor device comprising source and drain grid three ends and channel
It is placed in Ni3(HITP)2In reaction solution, and other places of the transistor device in addition to channel are covered using exposure mask, to original
The exposure mask is thrown off after the growth response of position, so that only growth in situ obtains Ni at the channel of the transistor device3
(HITP)2Film.
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| CN113437219A (en) * | 2021-06-09 | 2021-09-24 | 中国科学院合肥物质科学研究院 | Based on Ni3(HHTP)2Field effect transistor of conductive film and preparation method thereof |
| CN113791130A (en) * | 2021-08-27 | 2021-12-14 | 华中科技大学 | Ni3(HITP)2Field effect transistor biosensor and preparation method thereof |
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| US20170102358A1 (en) * | 2014-12-18 | 2017-04-13 | Agilome, Inc. | Chemically-sensitive field effect transistors, systems, and methods for manufacturing and using the same |
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| US20170102358A1 (en) * | 2014-12-18 | 2017-04-13 | Agilome, Inc. | Chemically-sensitive field effect transistors, systems, and methods for manufacturing and using the same |
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| GUODONG WU, ET AL: "Porous Field-Effect Transistors Based on a Semiconductive Metal−Organic Framework", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437219A (en) * | 2021-06-09 | 2021-09-24 | 中国科学院合肥物质科学研究院 | Based on Ni3(HHTP)2Field effect transistor of conductive film and preparation method thereof |
| CN113791130A (en) * | 2021-08-27 | 2021-12-14 | 华中科技大学 | Ni3(HITP)2Field effect transistor biosensor and preparation method thereof |
| CN113791130B (en) * | 2021-08-27 | 2023-03-10 | 华中科技大学 | Ni 3 (HITP) 2 Field effect transistor biosensor and preparation method thereof |
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