CN106927689A - A kind of oxide semiconductor thin-film and its preparation technology - Google Patents
A kind of oxide semiconductor thin-film and its preparation technology Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 71
- 239000004065 semiconductor Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000005516 engineering process Methods 0.000 title description 12
- 239000010408 film Substances 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims abstract description 13
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- 238000000137 annealing Methods 0.000 claims description 19
- 229910052706 scandium Inorganic materials 0.000 claims description 10
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims 1
- TWFKOYFJBHUHCH-UHFFFAOYSA-K diperchloryloxyindiganyl perchlorate Chemical compound [In+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O TWFKOYFJBHUHCH-UHFFFAOYSA-K 0.000 claims 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 24
- 239000001301 oxygen Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 10
- 238000002161 passivation Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052765 Lutetium Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- BYHSEJHLJMBVBG-UHFFFAOYSA-N [In].Cl(=O)(=O)(=O)O Chemical compound [In].Cl(=O)(=O)(=O)O BYHSEJHLJMBVBG-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D30/00—Field-effect transistors [FET]
- H10D30/60—Insulated-gate field-effect transistors [IGFET]
- H10D30/67—Thin-film transistors [TFT]
- H10D30/674—Thin-film transistors [TFT] characterised by the active materials
- H10D30/6755—Oxide semiconductors, e.g. zinc oxide, copper aluminium oxide or cadmium stannate
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Thin Film Transistor (AREA)
Abstract
本发明的种氧化物半导体薄膜及其制备工艺，薄膜成分为M2xIn2‑2xO3‑δ，且成分中不包括Zn和Sn，其中M为元素周期表中的ⅢB族元素，0.001≤x≤0.3，0≤δ＜3，采用水溶液制备，并且水溶液中不含碳元素。采用In盐和M盐的水溶液作为前驱体溶液进行水解反应，再对水解反应后的溶液进行成膜，成膜后在温度不高于300摄氏度的条件下退火制备而成。水溶液的溶质为硝酸盐、氯化物、氢氧化物或者高氯酸盐中的一种。本发明的氧化物半导体薄膜的制备方法所制备的薄膜，具有较高的电子迁移率；同时又能通过调节IIIB族元素的含量调节载流子浓度，关断性能良好、稳定性好、制备工艺简单、适用性强、环保。
In the oxide semiconductor film of the present invention and its preparation process, the composition of the film is M 2x In 2-2x O 3-δ , and Zn and Sn are not included in the composition, wherein M is a group IIIB element in the periodic table of elements, and 0.001≤ x≤0.3, 0≤δ<3, prepared by using an aqueous solution, and the aqueous solution does not contain carbon elements. The aqueous solution of In salt and M salt is used as the precursor solution for hydrolysis reaction, and then the solution after hydrolysis reaction is formed into a film, and then annealed at a temperature not higher than 300 degrees Celsius after film formation. The solute of the aqueous solution is one of nitrate, chloride, hydroxide or perchlorate. The thin film prepared by the preparation method of the oxide semiconductor thin film of the present invention has high electron mobility; at the same time, the carrier concentration can be adjusted by adjusting the content of group IIIB elements, and the shutdown performance is good, the stability is good, and the preparation process Simple, adaptable and environmentally friendly.
Description
Technical field
The present invention relates to semiconductor materials and devices technical field, more particularly to a kind of oxide semiconductor thin-film and its
Preparation technology.
Background technology
In recent years, in FPD especially in ORGANIC ELECTROLUMINESCENCE DISPLAYS (OLED) field, based oxide semiconductor
Thin film transistor (TFT) (TFT, Thin Film Transistor) be increasingly taken seriously.
Material currently used for the semiconductor channel layer of the thin film transistor (TFT) of FPD is mainly silicon materials, including amorphous
Silicon (a-Si：H), polysilicon, microcrystal silicon etc..But amorphous silicon film transistor exist it is low to photaesthesia, mobility (<1cm2/
Vs) and stability difference the shortcomings of；Although polycrystalline SiTFT is with mobility higher, because the influence of crystal boundary is led
Its electricity lack of homogeneity is caused, further, since polysilicon preparation temperature is high, high cost, be difficult to large area crystallization, it is limited flat
Plate show in application；And microcrystal silicon exists and prepares that difficulty is big, crystal grain control technology difficulty is high, it is not easy to realize large area scale
The defect of volume production.
Oxide semiconductor has carrier mobility (1~100cm higher2/ Vs), to visible transparent the advantages of,
The TFT substrate field of FPD, the trend for having the thin film transistor (TFT) of replacement tradition silicon technology preparation.
In the prior art, most of oxide semiconductor material be all with ZnO as matrix, be further incorporated into In, Ga, Al or
The elements such as Sn.There is the difficult defect of shut-off in the thin film transistor (TFT) of such oxide semiconductor material, i.e., when grid voltage is zero
Larger source-drain current is still present, device is in normally open, causes device quality not high enough.
In addition, such semi-conducting material is very sensitive to the water oxygen in air, the device without passivation layer is just swept and flyback
Transfer characteristic curve between hysteresis effect it is obvious.For being coated with passivation layer (the especially insulation material such as polymer, photoresist
Material) device, because extraneous oxygen further cannot be adsorbed on oxide semiconductor, cause the oxygen on oxide semiconductor surface
Room is increased, and device height easily occurs and leads state, i.e. oxide semiconductor presentation conductor features.This is allowed for based on this kind of oxidation
The thin film transistor (TFT) of thing semi-conducting material is typically only capable to use SiO2As passivation layer or etching barrier layer, and cannot be using can be with
The insulating materials such as the patterned polymer of chemical development or photoresist does passivation layer, increased process costs；Simultaneously because SiO2
Pliability it is poor, it is more difficult to in flexible substrate.
In addition, the above-mentioned oxide semiconductor material with ZnO as matrix generally needs more than 300 DEG C of after annealing
Temperature, and be typically only capable to be annealed under air or oxygen atmosphere, because the oxygen in the external world generally will could be empty with oxygen at 300 DEG C or so
Position in cationoid reaction and effectively fill Lacking oxygen.If annealed in nitrogen or inert gas, can be because cannot obtain
Obtain oxygen and cause height to lead phenomenon.300 DEG C of annealing temperature is relatively low for glass substrate, but for flexible substrate
For, it has been over the maximum temperature that most of flexible substrate material can bear.
Patent document (CN 201310276865.6) discloses a kind of oxide semiconductor thin-film, and composition is M2xIn2- 2xO3-δAnd do not include that Zn and Sn, wherein M are III B races element in the periodic table of elements, 0.001≤x≤0.3,0≤δ ＜ in composition
3.However, this film is prepared, it is necessary to the vacuum equipment of costliness by the method for sputtering, preparation cost is higher.
Non-patent literature (Adv.Electron.Mater.2015,1,1500146) discloses a kind of using solution preparation
The In of Sc, Y, La doping2O3The method of film, but the method uses organic solvent, and with the addition of some have it is inflammable and explosive
The fuel of property reduces annealing temperature, not only not environmentally, and carbon can be caused to remain.
Therefore, in view of the shortcomings of the prior art, to provide a kind of oxide semiconductor thin-film and its preparation technology existing to overcome
Technical deficiency is very necessary.
The content of the invention
There is provided that a kind of turn-off performance is good it is an object of the invention to avoid the deficiencies in the prior art part, can be applicable
In the oxide semiconductor thin-film of flexible substrate material, it is the channel layer materials for thin film transistor (TFT), with turn-off performance
Well, the characteristics of good stability, preparation process is simple, strong applicability.
Above-mentioned purpose of the invention is realized by following technological means.
A kind of preparation technology of oxide semiconductor thin-film is provided, thin film composition is M2xIn2-2xO3- δ,And without Zn and Sn,
Wherein M is III B races element in the periodic table of elements, and 0.001≤x≤0.3,0≤δ ＜ 3, the aqueous solution using In salt and M salt is made
For precursor solution is hydrolyzed reaction, then film forming is carried out to the solution after hydrolysis, being not higher than 300 in temperature after film forming takes the photograph
Annealing is prepared under conditions of family name's degree.
Preferably, the solute of the aqueous solution is the one kind in nitrate, chloride, hydroxide or perchlorate.
Another preferred, the solute of the aqueous solution includes nitrate and perchlorate simultaneously.
Another preferred, the solute of the aqueous solution is at least two materials in nitrate, chloride, hydroxide；Or
The solute of the aqueous solution is at least two materials in perchlorate, chloride, hydroxide.
Preferably, not carbon elements in the aqueous solution.
Preferably, the III B races element be Sc, Y, Ac, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,
The element of one kind or any two or more combinations in Yb or Lu；
M2xIn2-2xO3-δPrepare specifically with the aqueous solution of indium nitrate, villaumite indium or perchloric acid indium as precursor solution,
With with one kind in Sc, Y, Ac, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu or any two kinds
More than the aqueous solution of nitrate, villaumite or perchlorate of element be hydrolyzed reaction for precursor solution.
Preferably, the III B races element is Nd or Sc.
It is furthermore preferred that the III B races element is Sc.
Preferably, the preparation technology of above-mentioned oxide semiconductor thin-film, specifically using drop coating, spin coating, blade coating, spraying or print
The method of brush carries out film forming.
Another preferred, the preparation technology of above-mentioned oxide semiconductor thin-film, annealing temperature is not higher than 230 degrees Celsius.
Preferably, when above-mentioned precursor solution is villaumite, coordinate ultraviolet light or corona treatment, and annealed, move back
Fiery temperature is less than 200 degrees Celsius；
The atmosphere gas of annealing are air or inert gas.
Present invention simultaneously provides a kind of oxide semiconductor thin-film, it is prepared from by above-mentioned preparation technology, for making
It is the channel layer of thin film transistor (TFT).
(1) film prepared by the preparation method of oxide semiconductor thin-film of the invention, with electron transfer higher
Rate；Carrier concentration can be adjusted by adjusting the content of IIIB races element again simultaneously, so as to regulate and control based on oxide of the invention
The threshold voltage of the thin film transistor (TFT) of semiconductor film material.
(2) film prepared by the preparation method of oxide semiconductor thin-film of the invention to the water in air, oxygen less
Sensitivity, the thin film transistor (TFT) of the non-passivation layer protection based on oxide semiconductor film materials of the invention is just swept and flyback
Hysteresis effect between transfer characteristic curve is smaller；Meanwhile, thin film transistor (TFT) is insensitive to passivation material, can directly using poly-
Compound or photoresist insulating materials are passivated, and reduce process costs.
(3) the preparation method after annealing temperature of oxide semiconductor thin-film of the invention is relatively low, can be compatible with flexible substrate；
And being annealed under nitrogen or inert gas atmosphere can still keep characteristic of semiconductor, anti-attenuation higher is shown.
(4) film prepared by the preparation method of oxide semiconductor thin-film of the invention, mixes band gap after III B races element
Broadening, increases photostability.
(5) film prepared by the preparation method of oxide semiconductor thin-film of the invention, due to In2O3With unit of IIIB races
The trivalent of element belongs to bixbyite structure, would not heavy damage In after so adulterating2O3Original lattice, favorably
In reduction defect；Simultaneously as the main valence state of the main valence state of ion of IIIB races element and In is in trivalent, so, mix
The more than needed of electronics is not resulted in after entering, is conducive to reducing carrier concentration.
(6) preparation method of oxide semiconductor thin-film of the invention to be used do not contain in the aqueous solution, and the aqueous solution and appointed
What organic matter, so not only environmental protection, can also reduce carbon residual, reduce annealing temperature.
Brief description of the drawings
Using accompanying drawing, the present invention is further illustrated, but content in accompanying drawing is not constituted to any limit of the invention
System.
Fig. 1 is the X-ray diffractogram of the film of the different x contents prepared by the embodiment of the present invention 2.
Fig. 2 is the transfer characteristic curve of the thin film transistor (TFT) of the different x contents prepared by the embodiment of the present invention 2.
Fig. 3 is the bias stability figure of the thin film transistor (TFT) of the different x contents prepared by the embodiment of the present invention 2.
Fig. 4 is the X-ray diffractogram of the different film prepared by the embodiment of the present invention 3.
Fig. 5 is the transfer characteristic curve of the thin film transistor (TFT) that the embodiment of the present invention 3 is based on different Sc contents x.
Fig. 6 is the bias stability of the thin film transistor (TFT) that the embodiment of the present invention 3 is based on different Sc contents x.
Fig. 7 is the x-ray photoelectron energy spectrum diagram of the different Sc contents prepared by the embodiment of the present invention 3.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1.
A kind of preparation technology of oxide semiconductor thin-film, thin composition is M2xIn2-2xO3-δAnd in composition include Zn and
Sn, wherein M are III B races element in the periodic table of elements, 0.001≤x≤0.3,0≤δ ＜ 3, using In salt and the aqueous solution of M salt
It is hydrolyzed reaction as precursor solution, then film forming is carried out to the solution after hydrolysis, 300 is not higher than in temperature after film forming
Annealing is prepared under conditions of degree Celsius.
III B races element is in Sc, Y, Ac, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu
A kind of element of or any two or more combinations.Preferably Nd or Sc, more preferably Sc.
The solute of the aqueous solution is the one kind in nitrate, chloride, hydroxide or perchlorate.The solute of the aqueous solution
To include nitrate and perchlorate performance more preferably simultaneously.
The solute of the aqueous solution can also be at least two materials in nitrate, chloride, hydroxide；Or the aqueous solution
Solute be at least two materials in perchlorate, chloride, hydroxide.
It is preferred that, not carbon elements in the aqueous solution.Any organic matter is not contained in the aqueous solution, so not only environmental protection, can be with
Reduce carbon residual, reduce annealing temperature.
M2xIn2-2xO3-δPreparation be specifically it is molten as presoma with the aqueous solution of indium nitrate, villaumite indium or perchloric acid indium
Liquid and with the one kind in Sc, Y, Ac, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu or any two
The aqueous solution of the nitrate, villaumite or perchlorate of the element of kind of the above is hydrolyzed reaction for precursor solution.Specifically adopt
With the method film forming of drop coating, spin coating, blade coating, spraying or printing.
During precursor solution selection villaumite, coordinate ultraviolet light or corona treatment, and annealed, annealing temperature is small
In 200 degrees Celsius.The atmosphere gas of annealing are air or inert gas.
The prepared oxide semiconductor thin-film composition of the preparation method of the oxide semiconductor thin-film includes unit of III B races
Do not include Zn and Sn in element and In, and composition, be with In2O3It is the semiconductive thin film that matrix material is prepared from, matrix material is
The material of main component is accounted in finger compound.The carrier concentration of the oxide semiconductor thin-film is less than 5 × 1019cm-3, current-carrying
Sub- concentration is preferably smaller than 1017cm-3。
The radius of the radius ratio Zn atoms of In atoms is big, and its 5s track can be overlapped, with electron mobility higher, while
Even if In atoms also have the important performance also to form electron channel in noncrystalline state.Therefore In2O3Electrology characteristic pair
The degree relative insensitivity of its crystallization, therefore the uniformity of electric property can be improved.
The oxide semiconductor materials such as IZO, IGZO of the prior art are doped by matrix material of ZnO, due to In
Or the outer layer valence electron of Ga is more than Zn, as the Zn in In or Ga substitutions part ZnO, it may appear that valence electron more than needed so that material
The carrier concentration of material is big, even if still there is larger carrier concentration when Lacking oxygen is less.
From In unlike IZO, IGZO2O3It is to be adulterated by Lacking oxygen or surface state, as long as therefore reduction oxygen is empty
Position can be achieved with the control to its carrier concentration.The ionic element compared with strong (electronegativity is low) of selection mixes In2O3Can increase
M-O bond energys (M is metal ion), enhancing reduces Lacking oxygen defect to the attraction of oxygen.Simultaneously because In ions are trivalents, institute
The valence electron of surplus will not be produced with the element for mixing III race.Therefore, the element of III B races can simultaneously meet above-mentioned condition.
Due to being mixed with ionic III extremely strong B races element, with less Lacking oxygen, can effectively control carrier dense
Degree, so as to reduce electrical conductivity, shows characteristic of semiconductor.Additionally, oxide semiconductor material of the invention is due to its Lacking oxygen
It is few, it is difficult to be further incorporated into water, oxygen in air, therefore the oxide semiconductor material is insensitive to the water in air, oxygen.
It is demonstrated experimentally that the film prepared by the preparation method based on oxide semiconductor of the invention is protected for non-passivation layer
The hysteresis effect just swept and the transfer characteristic curve of flyback between of the thin film transistor (TFT) of shield is smaller；Meanwhile, it is to passivation layer material
Material is insensitive, directly can be passivated using polymer or photoresist insulating materials, can reduce process costs.
Because Lacking oxygen is few, the after annealing temperature of preparation method of the invention is relatively low, can be compatible with flexible substrate；And
Being annealed under nitrogen or inert gas atmosphere can still keep characteristic of semiconductor, show stability and anti-attenuation higher.
Additionally, compared to ZnO, In2O3With broader band gap, its band gap about 3.6eV, after III B races element is mixed, its
Band-gap energy further obtains broadening, can increase photopermeability, is suitable for Transparence Display, while can also reduce the suction of ultraviolet region
Receive, increase photostability.
It should be noted that the composition of the oxide semiconductor thin-film prepared by the present invention is not limited solely to complete chemistry
Measure the situation of matching, such as In2O3In O and In ratio (O/In) can be less than 3/2, correspond to the situation containing Lacking oxygen.Cause
This, the chemical formula of the oxide semiconductor thin-film composition is expressed as M2xIn2-2xO3-δ, wherein M be 3B races element, 0.001≤x≤
0.3,0≤δ ＜ 3.
It should be noted that in this manual also can be by the chemical formula of the oxide of non-fully stoichiometric match with complete
The chemical formula of full chemistry metering matching is stated, such as In2Oδ(0 ＜ δ ＜ 3) can be collectively referred to as In2O3。
The preparation method annealing temperature of oxide semiconductor thin-film of the invention is controllable to be less than 230 degrees Celsius.
Can mutually be replaced between film metal ion prepared by the preparation method of oxide semiconductor thin-film of the invention
Position and shared oxygen, it is also possible to there is the mixed crystal of different metal oxides.Oxide semiconductor thin-film of the invention can be monocrystalline,
The state of polycrystalline, crystallite or amorphous.
The preparation method of oxide semiconductor thin-film of the invention, is used as the system of the channel layer of thin film transistor (TFT)
It is standby, it is mainly used in the active matrix driving of organic light emitting display, liquid crystal display or Electronic Paper, it is also possible to for integrated circuit.
Embodiment 2.
A kind of preparation method of oxide semiconductor thin-film, the chemical formula of the oxide semiconductor thin-film composition is expressed as
Nd2xIn2-2xO3-δ, x selection 0.02,0.05 and 0.1 3 kind.Precursor solution is passed through using inidum chloride and the aqueous solution of neodymium chloride
The method film forming of spin coating, UV treatment again afterwards, then anneal 180 degrees Celsius in air atmosphere.
(x=0 represents non-impurity-doped In to the different x that accompanying drawing 1 shows prepared by the present embodiment2O3) film X-ray diffraction
(XRD) figure, it can be seen that when Nd amounts less (x=0.02) is mixed, In2O3Lattice structure keep preferable, illustrate a small amount of Nd
Will not heavy damage In2O3Lattice structure.But when Nd amounts more (x >=0.05) is mixed, In2O3Lattice damage it is serious, mainly
It is due to Nd3+Radius it is too big, doping is too high to cause serious lattice dilatation.
Prepared film is used for the channel layer of thin film transistor (TFT), and accompanying drawing 2 shows above-mentioned based on the thin of different Nd contents x
The transfer characteristic curve of film transistor (TFT), the performance parameter of TFT is listed in table one.As can be seen that the increasing of the incorporation with Nd
Many, the threshold voltage of TFT illustrates that mixing Nd can suppress In to forward flow2O3Middle superfluous intrinsic carrier.Here threshold value
Voltage is defined as：In the curve of the logarithm relative to grid current of drain current, when drain current just starts to be substantially increased pair
The value of the grid voltage answered, all " threshold voltages " mentioned all are defined using this in this specification.Additionally, mixing TFT after Nd
The reduction of device subthreshold swing, illustrates to mix the defect that Nd can be reduced in channel layer, improves stability.But mix the amount mistake of Nd
Strict destruction, TFT hydraulic performance declines can be caused when many to lattice.
The Nd of table one2xIn2-2xO3-δThe performance parameter of TFT
Accompanying drawing 3 shows prepared Nd2xIn2-2xO3-δThe bias stability of TFT, it can be seen that during x=0.02, threshold value
The drift value of voltage is minimum, but when Nd amounts more (x >=0.05) is mixed, stability can decline.
In sum, the thin film transistor (TFT) prepared by semiconductive thin film of the invention has that turn-off performance is good, stability
The characteristics of good, preparation process is simple, strong applicability, environmental protection.
Embodiment 3.
A kind of preparation method of oxide semiconductor thin-film, the chemical formula of composition is expressed as Sc2xIn2-2xO3-δ, x selections
0.02nd, 0.05 and 0.1 3 kind.Precursor solution, by the method film forming of spin coating, is moved back using indium nitrate and the aqueous solution of scandium nitrate
230 degrees Celsius of fiery temperature.
(x=0 represents non-impurity-doped In to the different x that accompanying drawing 4 shows prepared by the present embodiment2O3) film X-ray diffraction
(XRD) figure, it can be seen that hardly to In after incorporation Sc2O3Lattice structure, this is mainly due to Sc3+Radius and In3+
Radius it is close, the lattice dilatation for hardly causing.
Prepared film is used for the channel layer of thin film transistor (TFT), and accompanying drawing 5 shows above-mentioned based on the thin of different Sc contents x
The transfer characteristic curve of film transistor (TFT), the performance parameter of TFT is listed in table two.As can be seen that the increasing of the incorporation with Sc
Many, the threshold voltage of TFT illustrates that mixing Sc can suppress In to forward flow2O3Middle superfluous intrinsic carrier.Additionally, mixing
TFT devices subthreshold swing reduction after Sc, illustrates to mix the defect that Sc can be reduced in channel layer, improves stability.
The Sc of table two2xIn2-2xO3-δThe performance parameter of TFT
Accompanying drawing 6 shows prepared Sc2xIn2-2xO3-δThe bias stability of TFT, as Sc dopings increase, TFT devices
The stability of part is constantly improve, illustrates that mixing Sc can suppress Lacking oxygen, reduce defect.
Accompanying drawing 7 shows x-ray photoelectron power spectrum (XPS) figure of prepared different Sc contents, it can be seen that with Sc
Doping increases, and the corresponding swarming of Lacking oxygen (530.4eV, Peak2) is persistently reduced, and illustrates that mixing Sc can effectively suppress oxygen sky
Position is visible, using Sc2xIn2-2xO3-δFilm can effectively control the dense of intrinsic carrier as the thin film transistor (TFT) of channel layer
Degree, adjusting threshold voltage, the characteristics of with stable performance.
In sum, the thin film transistor (TFT) prepared by semiconductive thin film of the invention has that turn-off performance is good, stability
The characteristics of good, preparation process is simple, strong applicability, environmental protection.
Embodiment 4.
A kind of preparation method of oxide semiconductor thin-film, the chemical formula of composition is expressed as Sc2xIn2-2xO3-δ, x selections
0.05.Precursor solution using perchloric acid indium and the aqueous solution of scandium nitrate, by the method film forming of spin coating, take the photograph by annealing temperature 200
Family name's degree.The channel layer that prepared film is used for thin film transistor (TFT) obtains 15.7cm2V–1s–1Mobility.
In sum, the thin film transistor (TFT) prepared by semiconductive thin film of the invention has that turn-off performance is good, stability
The characteristics of good, preparation process is simple, strong applicability, environmental protection.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope, although being explained in detail to the present invention with reference to preferred embodiment, one of ordinary skill in the art should manage
Solution, technical scheme can be modified or equivalent, without deviating from technical solution of the present invention essence and
Scope.
Claims (10)
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Application publication date: 20170707 |