CN104201112A - Preparation method for water solution thin film transistor - Google Patents
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- CN104201112A CN104201112A CN201410505093.3A CN201410505093A CN104201112A CN 104201112 A CN104201112 A CN 104201112A CN 201410505093 A CN201410505093 A CN 201410505093A CN 104201112 A CN104201112 A CN 104201112A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000010409 thin film Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010408 film Substances 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 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 abstract description 7
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 7
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 238000004528 spin coating Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000280 densification Methods 0.000 claims description 2
- 238000005906 dihydroxylation reaction Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- ZEWMZYKTKNUFEF-UHFFFAOYSA-N indium;oxozinc Chemical compound [In].[Zn]=O ZEWMZYKTKNUFEF-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a 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
- H01L29/66969—Multistep manufacturing processes of devices having semiconductor bodies not comprising group 14 or group 13/15 materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02192—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
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- Thin Film Transistor (AREA)
Abstract
The invention belongs to the technical field of semiconductor thin film transistor preparation, and relates to a preparation method for a water solution thin film transistor. Firstly, yttrium nitrate is dissolved in deionized water, and a zirconia precursor solution is formed by magnetic force mixing; then, the surface of a low resistance silicon base is cleaned, and is coated with the precursor solution in a rotation manner; a Y2O3 film sample is obtained through baking and low temperature annealing; zinc nitrate and indium nitrate are respectively dissolved in deionized water, and an IZO water solution is formed through mixing; the Y2O3 film surface is coated with the IZO water solution in a rotation manner, is subjected to solidification treatment and low temperature annealing, so that an IZO gutter channel layer is obtained; finally, the vacuum thermal evaporation technology is adopted to prepare a metal source and an electric leakage pole on the IZO gutter channel layer, and the water solution thin film transistor based on ultrathin Y2O3 and high K dielectric layer is obtained. The overall embodiment is low in price; the technology is simple, the principle is reliable, the product performance is good, the preparation is environment-friendly, and the application prospect is wide.
Description
Technical field:
The invention belongs to semiconductor thin-film transistor preparing technical field, relate to a kind of preparation method based on aqueous solution thin-film transistor, particularly a kind of taking indium zinc oxide (InZnO) as channel layer with ultra-thin yittrium oxide (Y
2o
3) be the preparation technology of the environmental type thin-film transistor based on aqueous process of high k dielectric layer.
Background technology:
At present, thin-film transistor (Thin Film Transistor, TFT) has been brought into play important function in driven with active matrix liquid crystal display device (Active Matrix Liquid Crystal Display, AMLCD).From low temperature amorphous silicon TFT to high temperature polysilicon TFT, its technology is more and more ripe, application also from can only drive LCD (Liquid Crystal Display) to develop into not only can to drive LCD but also can driving OLED (Organic Light Emitting Display), Electronic Paper even; Along with semiconductor process technology improves constantly, Pixel Dimensions constantly reduces, the resolution of display screen is also more and more higher, TFT is as driving the switch application of pixel in the display devices such as liquid crystal display (TFT-LCD), wherein the size of grid dielectric material energy gap determines the size of leakage current, and its relative dielectric constant determines the size (being energy consumption size) of device subthreshold swing; Along with the development of large scale integrated circuit, constantly reduce as the characteristic size of the metal oxide semiconductor transistor of si-substrate integrated circuit core devices always, it reduces rule and follows Moore's Law; The existing lithographic dimensioned 28nm that reached, CMOS grid equivalent oxide thickness drops to below 1nm, the thickness of gate oxide approaches atomic distance (IEEEElectron Device Lett.2004,25 (6): 408-410), cause tunnel effect along with reducing of equivalent oxide thickness, research shows silicon dioxide (SiO
2) thickness while reducing to 1.5nm by 3.5nm grid leakage current by 10
-12a/cm
2increase to 10A/cm
2(IEEE Electron Device Lett.1997,18 (5): 209-211); Larger leakage current can cause high power consumption and corresponding heat dissipation problem, and this all causes adverse influence for device integrated level, reliability and life-span, is therefore badly in need of the high dielectric material replacement traditional Si O that research and development make new advances
2, in prior art, in MOS integrated circuit technology, extensively adopt high-k (high k) grid dielectric increases capacitance density and reduces grid leakage current, and high k material is because of its large dielectric constant, with SiO
2there is in the situation of same equivalent gate oxide thickness (EOT) its actual Thickness Ratio SiO
2large is many, thereby has solved SiO
2the quantum tunneling effect producing because approaching the physical thickness limit.
The novel high-k dielectric material that has become at present study hotspot comprises ATO (Advanced Material, 24,2945,2012), Al
2o
3(Nature, 489,128,2012), ZrO
2(Advanced Material, 23,971,2011), WO
3(Applied Physics Letters, 102,052905,2013) and Ta
2o
5(Applied Physics Letters, 101,261112,2012) etc., TFT device is film-type structure, dielectric constant, compactness and the thickness of its gate dielectric layer is very large to transistorized performance impact, at numerous SiO
2in grid dielectric substitute, zirconia (Y
2o
3) there is good reliability as high-k dielectric material, it has larger dielectric constant (14-18), wider band gap (5.5-6.0eV), electronics and hole are had to proper passage barrier height (being greater than 1eV), there is good Lattice Matching with Si surface, can be compatible mutually with traditional CMOS technique; Therefore, Y
2o
3be supposed to substitute traditional grid dielectric material, become the strong candidate of the high k grid of TFT of new generation dielectric material; And, consider new direction-printing electronic device of microelectronic component development in the future, utilizing chemical solution technology to prepare film will be a well selection, chemical solution technology is subject to extensive use in the preparation technology of superfines, film coating, fiber and other material, it has advantages of that it is unique: in its reaction each component be blended in intermolecular carrying out, thereby the particle diameter of product is little, uniformity is high; Course of reaction is easy to control, and can obtain the product that some are difficult to obtain with additive method, and reaction is carried out at low temperatures in addition, has avoided the appearance of high temperature dephasign, makes the purity of product high.
While adopting at present chemical solution technology to prepare film, the organic system solution that adopts as presoma more, and the method not only increases experimental cost, and its waste liquid destroys natural environment, is unfavorable for aim sustainable, environmental protection; Find a kind of full aqueous chemical solwution method and prepare the new approaches of thin-film transistor, in the preparation process of whole device, only have the nitrate of metal and deionized water as reaction source, adopt deionized water to substitute traditional organic solution (EGME etc.) as solvent, form novel aqueous solution, aqueous solution has the advantages such as nontoxic, environmental protection, cheapness than conventional organic solution, is technical assignment anxious to be resolved in the industry; In addition owing to being electrostatical binding between solute cation and hydrone in aqueous solution, there is more weak combination energy than covalent bonds mode in organic solution, therefore the film that adopts the spin coating of aqueous solution method to prepare has lower decomposition temperature, so utilize aqueous solution to prepare the technical task that reliability is high, reproducible, the thin-film transistor of low-temperature decomposition is just becoming industrial quarters and scientific research circle is furtherd investigate.
At present, adopt amorphous oxides indium zinc oxygen (IZO), indium gallium zinc oxygen (IGZO), indium oxide (In
2o
3) material is as the preparation of thin film transistor channel layer and the existing open source literature of application technology, large quantity research has done in the states such as Japan and Korea S.; IZO relies on its high mobility, amorphous state, high permeability (visible ray >80%) to become the strong candidate of semiconductor channel layer material; Known by consulting of Patents, document, utilize aqueous solution method to prepare TFT channel layer and have no report, based on water-based Y
2o
3nobody sets foot in the full water-based TFT device of high k dielectric layer especially; Consider the requirement of future " flexible display device " to low temperature in thin film preparation process process, guarantee in TFT preparation process that temperature is lower than 300oC, IZO/Y prepared by above-mentioned technique
2o
3the TFT device of structure not only has higher carrier mobility, and thering is the feature (being greater than 80% in visible light wave range transmitance) of the high grade of transparency, its TFT, as the pixel switch of AMLCD, will improve the aperture opening ratio of active matrix greatly, improve brightness, reduce power consumption simultaneously; Its whole soln preparation technology does not rely on expensive vacuum coating equipment in addition, and cost of manufacture is further reduced, and these advantages make its transparent electron display device field in future have very wide potential market.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, seek design and provide a kind of with ultra-thin yittrium oxide (Y
2o
3) for the preparation method of high k dielectric layer and the full water-based thin-film transistor taking IZO as channel layer, first select low-resistance silicon as substrate and gate electrode, adopt respectively aqueous solution and the Low Temperature Thermal method combining of annealing to prepare ultra-thin Y
2o
3(<20nm) the IZO semiconductor channel layer of gate dielectric layer and high permeability, high mobility, thus prepare high performance thin-film transistor, and make its electric property meet the requirement of display to thin-film transistor (TFT).
To achieve these goals, concrete technology of the present invention comprises the following steps:
(1), Y
2o
3the preparation of precursor solution: by yttrium nitrate Y (NO
3)
3h
2o is dissolved in deionized water, stirs the Y that forms clear for 1-24 hour at 20-90 DEG C of lower magnetic force
2o
3precursor solution, wherein Y
2o
3precursor solution concentration is 0.01-0.5mol/L;
(2), Y
2o
3the preparation of film sample: adopt conventional plasma cleaning method to clean low-resistance surface of silicon, on low-resistance silicon substrate after cleaning, adopt the precursor solution of conventional spin coating technique spin coating step (1) preparation, first even glue 4-8 second under 400-600 rev/min, even glue 15-30 second under 2000-5000 rev/min again, spin coating number of times is 1-3 time, each spin coating thickness 5-10nm; Film after spin coating is put into and on roasting Jiao Tai, carries out temperature control 100-200 DEG C cure, cure test sample; Again the sample after curing is carried out to 300 DEG C of process annealing 1-3 hour, realize dehydroxylation and metal oxide densification, obtain Y
2o
3film sample;
(3), the preparation of IZO channel layer: by zinc nitrate Zn (NO
3)
2with indium nitrate In (NO
3)
3be dissolved in respectively in deionized water the IZO aqueous solution that the concentration that at room temperature stirs 1-24 hour formation clear is 0.01-0.5mol/L, In in aqueous solution
3+: Zn
2+be 1～9:1; The Y obtaining in step (2)
2o
3film sample surface utilizes spin coating technique spin coating IZO aqueous solution, first even glue 4-8 second under 400-600 rev/min, then under 2000-5000 rev/min even glue 15-30 second, spin coating number of times is 1-3 time, spin coating thickness is 5-10nm at every turn; Film after spin coating is put into 120-150 DEG C of roasting Jiao Tai and is cured and puts into Muffle furnace after processing and carry out 200-300 DEG C of process annealing and process 1-5 hour, prepare IZO channel layer;
(4), the preparation of source, drain electrode: utilize conventional vacuum thermal evaporation utilization mask plate to prepare source metal and drain electrode on IZO channel layer, obtain based on ultra-thin Y
2o
3high k dielectric layer based on aqueous solution thin-film transistor.
The deionized water resistivity >18M Ω cm relating in step of the present invention (1).
The plasma clean method relating in step of the present invention (2) adopts oxygen or argon gas as purge gas, and its power is 20-60Watt, and scavenging period is 20-200s, and the intake of working gas is 20-50SCCM.
The electrode raceway groove length-width ratio of thin-film transistor prepared by step of the present invention (4) is 1:4～20, and thermal evaporation electric current is 30-50A; Source, the very Al that leaks electricity, Au or Ni metal electrode, thickness of electrode is 50-200nm.
The present invention compared with prior art, there is following advantage: the one, the semiconductor channel layer in thin-film transistor and high k dielectric layer all utilize chemical solution method to prepare, chemical solution method is with low cost, and its preparation process does not need high vacuum environment, in air, can carry out; Reaction can be carried out at low temperatures, avoids the appearance of high temperature dephasign when reducing costs; The 2nd, using plasma cleans substrate surface, and while increasing spin coating, precursor solution, at the adhesive force of substrate, makes the film sample surface homogeneous and smooth more after spin coating; The 3rd, adopt aqueous solution method and the Low Temperature Thermal mode combining of annealing to obtain novel grid dielectric material Y
2o
3, avoid the demand of traditional chemical solution methods film-forming process for high temperature (>500 DEG C), make the Y of preparation
2o
3dielectric layer can be prepared in plastic, for important foundation is established in application flexible, transparent display part; The 4th, the Y making
2o
3the physical thickness of high k gate dielectric layer is less than 20nm, and the low-leakage current simultaneously having meets the integrated demand for device size of microelectronics well; Y
2o
3the high permeability (visible light wave range approaches 90%) that film itself has, meets the requirement of transparent electronics to material self; The Y making
2o
3film is amorphous state, can prepare dielectric layer by Large-Area-Uniform; The 5th, in thin-film transistor, insulating barrier and channel layer all utilize aqueous solution method preparation, utilize deionized water to have the advantages such as nontoxic, environmental protection than conventional organic solvents as solvent phase; Meanwhile, aqueous solution is less demanding to ambient humidity, therefore further reduces preparation cost; Finally, because deionized water does not have corrosivity, when being spun to Y
2o
3on gate dielectric layer time, can not corrode Y
2o
3surface, is therefore beneficial to formation interface more clearly, and this is most important for thin-film transistor performance high-performance electricity performance; The 6th, the high permeability (visible light wave range is greater than 80%) that utilizes aqueous solution to prepare IZO semiconductive thin film itself to have, meets the requirement of transparent electronics; The advantage that simultaneously prepared by low temperature (<300 DEG C) is compatible mutually with the low temperature manufacturing technology that flat panel display requires; Its General Implementing scheme cost is low, and technique is simple, and principle is reliable, good product performance, and preparation environmental friendliness, has a extensive future, and preparing high performance thin-film transistor for large area provides feasible scheme.
Brief description of the drawings:
Fig. 1 be the present invention prepare based on Y
2o
3the structural principle schematic diagram of the full water-based IZO thin-film transistor of high k dielectric layer.
Fig. 2 is water-based Y prepared by the present invention
2o
3the leakage current test curve figure of high k dielectric layer.
Fig. 3 is water-based Y prepared by the present invention
2o
3the capacity measurement curve chart of high k dielectric layer.
Fig. 4 is full water-based IZO/Y prepared by the present invention
2o
3the output characteristic curve figure of thin-film transistor, wherein grid bias V
gS=1.5V.
Fig. 5 is full water-based IZO/Y prepared by the present invention
2o
3the transfer characteristic curve figure of thin-film transistor, wherein source-drain voltage V
dS=1.0V.
Embodiment:
Also further illustrate by reference to the accompanying drawings the present invention below by specific embodiment.
Embodiment:
Yttrium nitrate, zinc nitrate and indium nitrate powder in the present embodiment are all purchased from Aladdin company, and purity is greater than 98%; Its bottom grating structure is with ultra-thin yittrium oxide (Y
2o
3) for high k dielectric layer and the preparation process based on aqueous solution thin-film transistor taking indium zinc oxide (IZO) film as channel layer as:
(1) adopt the spin coating of aqueous solution method to prepare ultra-thin Y
2o
3high k dielectric film:
Step 1: select the single-sided polishing low-resistance silicon of business purchase as substrate (ρ < 0.0015 Ω cm) and gate electrode, low-resistance silicon substrate is used hydrofluoric acid, acetone, alcohol Ultrasonic Cleaning substrate each 10 minutes successively, after repeatedly rinsing with deionized water, high pure nitrogen dries up;
Step 2: yttrium nitrate is dissolved in this mixed solution according to 0.2M, weighs deionized water 10mL, taking acetylacetone,2,4-pentanedione zirconium is 0.76g, after mixing, under the effect of magnetic agitation, stirring at room temperature forms clarification, transparent Y for 5.5 hours
2o
3precursor liquid;
Step 3: clean low-resistance silicon substrate is put into plasma clean chamber, and extracting to passing into purity after 0.5Pa until chamber is 99.99% oxygen, and controlling its power is 30Watt, and scavenging period is 120s, and when work, the intake of oxygen is 30SCCM;
Step 4: preparation Y
2o
3sample: the precursor solution of preparation in step 2 is spin-coated on the low-resistance silicon substrate cleaning, and spin coating number of times is 1～5 time, and when spin coating precursor solution, the parameter of sol evenning machine is set to: elder generation is in 500 revs/min of even glue 5 seconds, then in 5000 revs/min of even glue 25 seconds; After spin coating finishes, sample is put into the upper 150oC of roasting Jiao Tai and cures 10min, will solidify Y after treatment
2o
3sample is put into the processing of Muffle furnace process annealing, and annealing temperature is 300 DEG C, and annealing time is 1 hour, obtains Y
2o
3sample;
(2) utilize the spin coating of aqueous solution method to prepare IZO channel layer:
Step 1: indium nitrate and zinc nitrate powder are dissolved in respectively in deionized water to In
3+: Zn
2+=7:3, metal cation total concentration is 0.2M; In this experiment, measure deionized water 10mL, take respectively indium nitrate 0.42g and zinc nitrate 0.18g, after mixing, under the effect of magnetic agitation, stirring at room temperature 5.5 hours forms the IZO aqueous solution of clear;
Step 2: preparation In
2o
3channel layer: the indium nitrate aqueous solution of preparation in step 1 is spin-coated on to the Y processing
2o
3on sample, when spin coating, the parameter of sol evenning machine is set to: first in 500 revs/min of even glue 5 seconds, then, in 3000 revs/min of even glue 25 seconds, after spin coating finishes, sample is put into the processing of Muffle furnace process annealing, annealing temperature is for being respectively 230 DEG C, annealing time 4 hours;
(3) adopt Vacuum sublimation to prepare source, leak metal electrode:
By the mode of thermal evaporation, on IZO channel layer, prepare metal A l that 100nm is thick as source, drain electrode with the mask plate that breadth length ratio is 1000 μ m/250 μ m, thermal evaporation electric current is 40A, prepares Al/IZO/Y
2o
3the thin-film transistor of/Si structure;
(4) to the Al/IZO/Y making
2o
3the thin-film transistor test of/Si structure (Fig. 1); The water-based Y of preparation
2o
3the leakage current test of dielectric layer and capacity measurement curve are respectively as shown in Figures 2 and 3; The thin-film transistor output characteristic curve making as shown in Figure 4; The transfer characteristic curve corresponding to thin-film transistor of preparation as shown in Figure 5; Fig. 2, Fig. 4, Fig. 5 curve are obtained by Keithley 2634B semiconductor parametric tester; Fig. 3 curve is obtained by Agilent 4155C test.
Claims (4)
1. the preparation method based on aqueous solution thin-film transistor, is characterized in that concrete technology comprises the following steps:
(1), Y
2o
3the preparation of precursor solution: by yttrium nitrate Y (NO
3)
3h
2o is dissolved in deionized water, stirs the Y that forms clear for 1-24 hour at 20-90 DEG C of lower magnetic force
2o
3precursor solution, wherein Y
2o
3precursor solution concentration is 0.01-0.5mol/L;
(2), Y
2o
3the preparation of film sample: adopt conventional plasma cleaning method to clean low-resistance surface of silicon, on low-resistance silicon substrate after cleaning, adopt the precursor solution of conventional spin coating technique spin coating step (1) preparation, first even glue 4-8 second under 400-600 rev/min, even glue 15-30 second under 2000-5000 rev/min again, spin coating number of times is 1-3 time, each spin coating thickness 5-10nm; Film after spin coating is put on roasting Jiao Tai and carries out curing of temperature control 100-200oC, cure test sample; Again the sample after curing is carried out to 300 DEG C of process annealing 1-3 hour, realize dehydroxylation and metal oxide densification, obtain Y
2o
3film sample;
(3), the preparation of IZO channel layer: by zinc nitrate Zn (NO
3)
2with indium nitrate In (NO
3)
3be dissolved in respectively in deionized water the IZO aqueous solution that the concentration that at room temperature stirs 1-24 hour formation clear is 0.01-0.5mol/L, In in aqueous solution
3+: Zn
2+be 1～9:1; The Y obtaining in step (2)
2o
3film sample surface utilizes spin coating technique spin coating IZO aqueous solution, first even glue 4-8 second under 400-600 rev/min, then under 2000-5000 rev/min even glue 15-30 second, spin coating number of times is 1-3 time, spin coating thickness is 5-10nm at every turn; Film after spin coating is put into 120-150 DEG C of roasting Jiao Tai and is cured and puts into Muffle furnace after processing and carry out 200-300 DEG C of process annealing and process 1-5 hour, prepare IZO channel layer;
(4), the preparation of source, drain electrode: utilize conventional vacuum thermal evaporation utilization mask plate to prepare source metal and drain electrode on IZO channel layer, obtain ultra-thin Y
2o
3high k dielectric layer based on aqueous solution thin-film transistor.
2. the preparation method based on aqueous solution thin-film transistor according to claim 1, is characterized in that the deionized water resistivity >18M Ω cm relating in step (1).
3. the preparation method based on aqueous solution thin-film transistor according to claim 1, it is characterized in that the plasma clean method relating in step (2) adopts oxygen or argon gas as purge gas, its power is 20-60Watt, scavenging period is 20-200s, and the intake of working gas is 20-50SCCM.
4. the preparation method based on aqueous solution thin-film transistor according to claim 1, is characterized in that the electrode raceway groove length-width ratio of thin-film transistor prepared by step (4) is 1:4～20, and thermal evaporation electric current is 30-50A; Source, leak electricity very Al, Au or Ni metal electrode, thickness of electrode is 50-200nm.
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Application publication date: 20141210 |