CN104009093B - A kind of preparation method of high k dielectric layer aqueous indium oxide film transistor - Google Patents

A kind of preparation method of high k dielectric layer aqueous indium oxide film transistor Download PDF

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CN104009093B
CN104009093B CN201410264881.8A CN201410264881A CN104009093B CN 104009093 B CN104009093 B CN 104009093B CN 201410264881 A CN201410264881 A CN 201410264881A CN 104009093 B CN104009093 B CN 104009093B
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spin coating
film transistor
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annealing
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CN104009093A (en
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单福凯
刘奥
刘国侠
孟优
谭惠月
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Qingdao University
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Abstract

The invention belongs to semiconductor thin-film transistor preparing technical field, relate to the preparation method of a kind of high k dielectric layer aqueous indium oxide film transistor, first acetylacetone,2,4-pentanedione zirconium is dissolved in dimethylformamide, is simultaneously introduced the ethanolamine with acetylacetone,2,4-pentanedione zirconium equimolar amounts and forms precursor solution as stabilizer；On low-resistance silicon substrate the most after cleaning, spin coating precursor solution obtains sample, is put under high voltage mercury lamp by sample and carries out the sample after ultraviolet lighting process obtains photo-annealing；Then the sample after photo-annealing is carried out annealing and obtain film sample；Then at the film sample surface spin coating In obtained2O3Aqueous solution obtains In2O3Channel layer；Last at In2O3Channel layer source prepared above, drain electrode, i.e. obtain thin film transistor (TFT)；Its general embodiment low cost, technique is simple, and principle is reliable, good product performance, prepares environmental friendliness, has a extensive future, and preparing high performance thin film transistor (TFT) for large area provides feasible scheme.

Description

A kind of preparation method of high k dielectric layer aqueous indium oxide film transistor
Technical field:
The invention belongs to semiconductor thin-film transistor preparing technical field, relate to a kind of high k dielectric The preparation method of layer aqueous indium oxide film transistor, particularly a kind of with aqueous Indium sesquioxide. (In2O3) it is channel layer and with ultra-thin zirconium oxide (ZrOx, 1 < x < 2) and it is the thin of high k dielectric layer The preparation method of film transistor.
Background technology:
In recent years, thin film transistor (TFT) (Thin Film Transistor, TFT) is at active square Battle array driving liquid crystal display device (Active Matrix Liquid Crystal Display, AMLCD) important function has been played in.From low temperature amorphous silicon TFT to high temperature polysilicon TFT, Technology is more and more ripe, and application is also from driving LCD (Liquid Crystal Display) develop into not only to drive LCD but also OLED (Organic Light can be driven Emitting Display), even Electronic Paper.Along with semiconductor process technology improves constantly, Pixel Dimensions constantly reduces, and the resolution of display screen is more and more higher, and TFT is as driving pixel Switch application in the display devices such as liquid crystal display (TFT-LCD), wherein grid dielectric material The size of energy gap determines the size of leakage current, and its relative dielectric constant then determines device The size (i.e. energy consumption size) of subthreshold swing.Along with the development of large scale integrated circuit, make Characteristic size one for the metal oxide semiconductor transistor of si-substrate integrated circuit core devices Straight constantly reduction, it reduces rule and follows Moore's Law.At present lithographic dimensioned has reached 28 Nm, CMOS gate equivalent oxide thickness drops to below 1nm, and the thickness of gate oxide is close Atomic distance (IEEE Electron Device Lett.2004,25 (6): 408-410), along with The reduction of equivalent oxide thickness and cause tunnel-effect, research shows silicon dioxide (SiO2) When thickness is reduced to 1.5nm by 3.5nm, grid leakage current is by 10-12A/cm2Increase to 10A/cm2 (IEEE Electron Device Lett.1997,18(5):209-211).Bigger electric leakage Stream can cause high power consumption and corresponding heat dissipation problem, and this is for device integration, reliability and longevity Life all adversely affects, and is therefore badly in need of the high dielectric material replacement tradition that research and development make new advances SiO2.At present, widely used high-k (high k) grid in MOS integrated circuit technology Dielectric increases capacitance density and reduces grid leakage current, and high-g value is normal because of its big dielectric Number, with SiO2In the case of having same equivalent gate oxide thickness (EOT), it is actual Thickness compares SiO2Big many, thus solve SiO2Because of produce close to the physical thickness limit Quantum tunneling effect.
The novel high-k dielectric material becoming study hotspot at present includes ATO (Advanced Material,24,2945,2012)、Al2O3(Nature,489,128,2012),ZrO2 (Advanced Material,23,971,2011)、WO3(Applied Physics Letters, 102,052905,2013) and Ta2O5(Applied Physics Letters,101,261112, 2012) etc..TFT device is membrane type structure, the dielectric constant of its gate dielectric layer, compactness Very big, at numerous SiO to the performance impact of transistor with thickness2In grid dielectric succedaneum, oxidation Zirconium (ZrOx) as high-k dielectric material, there is good reliability, it is normal that it has bigger dielectric Number (20-30), wider band gap (5.8eV) (Advanced Material, 23,971, 2011), electronics and hole are had proper passage barrier height (more than 1eV), Good Lattice Matching is had with Si surface, can be mutually compatible with traditional CMOS technology.Therefore, ZrOxIt is expected to substitute tradition grid dielectric material, becomes a new generation's TFT height k grid dielectric material The strong candidate of material.Moreover, it is contemplated that the new direction to microelectronic component development in the future prints Electronic device, utilizing sol-gel technique to prepare thin film will be a good selection, colloidal sol -gel technique superfines, film coating, fiber and other material preparation technology in by wide General application, the advantage that it has its uniqueness: its reaction in each component be blended in intermolecular carrying out, Thus the particle diameter of product is little, uniformity is high；Course of reaction is easily controllable, can get some and uses it His method is difficult to the product obtained, additionally react and carry out at low temperatures, it is to avoid high temperature dephasign Occur so that the purity of product is high.Therefore sol-gel technique is used to prepare ZrOxHigh k is situated between Conductive film, proposes one and uses ultraviolet light decomposition and low temperature (300 DEG C) thermal decomposition to combine Way decomposes ZrOxOrganic principle in thin film, the principle that wherein ultraviolet light decomposes is: utilize purple Oxygen in the UVC (200-275nm) of outside line and UVD wave band (100-200nm) and air Solid/liquid/gas reactions produces active oxygen, have strong oxidizing property active oxygen can at room temperature with C in thin film, N element reaction generates Cox、NOxGas thus depart from thin film；Meanwhile, ultraviolet light decomposition method Can improve film sample surface state (Applied Physics Letters, 102,192101, 2013) so that sample surfaces is finer and close, smooth, the roughness that gate dielectric layer surface is less Being conducive to the carrier migration on surface, the carrier mobility and the switch that improve TFT device ring Answer speed.Additionally, follow-up employing low temperature thermal decomposition processes ZrOxThin film can be prevented effectively from and partly lead The interlayer brought during body channel layer process annealing (< 300 DEG C) dissolves each other phenomenon；At channel layer Preparation process in, use distilled water to substitute traditional organic solution (ethylene glycol monomethyl ether etc.) conduct Solvent, forms novel aqueous solution, aqueous solution compared to conventional organic solution have nontoxic, Environmental protection, the advantage such as cheap；Additionally due to aqueous solution is quiet between solute cation and hydrone It is electrically coupled, compared to covalent bond combination in organic solution, there is more weak combination energy, therefore The thin film using aqueous solution method spin coating has lower decomposition temperature, utilizes aqueous solution skill Art prepare reliability semiconductive thin film high, reproducible, low-temperature decomposition just becoming industrial quarters and The technical field that scientific research circle is being furtherd investigate.
At present, amorphous oxides indium zinc oxygen (IZO), indium gallium zinc oxygen (IGZO), oxidation are used Indium (In2O3) material is disclosed literary composition as preparation and the application technology of thin film transistor channel layer Offering, numerous studies have been done by the state such as Japan and Korea S..In2O3By its high mobility (> 100cm2/V·s)、 High permeability (visible ray > 80%) becomes the strong candidate (IEEE of semiconductor channel layer material Electron Device Lett.31,567,2010).We pass through Patents, document Consult, utilize aqueous solution method to prepare TFT channel layer and rarely have report, based on ultra-thin ZrOx Aqueous In of high k dielectric layer2O3Nobody sets foot in TFT especially.In view of following " Flexible Displays Device " to the requirement of low temperature during thin film preparation process, we ensure that in TFT preparation process Temperature is less than 300 DEG C.In prepared by above-mentioned technique2O3/ZrOxThe TFT device of structure not only has Higher carrier mobility, and the feature with the high grade of transparency (passes through at visible light wave range Rate is more than 80%), its TFT, as the pixel switch of AMLCD, will be greatly improved active matrix Aperture opening ratio, improve brightness, reduce power consumption simultaneously；Additionally its whole soln preparation technology is independent of Expensive vacuum coating equipment so that cost of manufacture reduces further, and these advantages make it not There is the most wide potential market in the transparent electron display device field come.
Summary of the invention:
It is an object of the invention to the shortcoming overcoming prior art to exist, seek design and provide one Plant with ultra-thin zirconium oxide (ZrOx) it is high k dielectric layer and with aqueous Indium sesquioxide. (In2O3) it is raceway groove The preparation method of the high performance thin film transistor of layer, first selects low-resistance silicon as substrate and grid electricity Pole, the mode using sol-gel technique, photo-annealing and Low Temperature Thermal annealing to combine is prepared super Thin ZrOx(< 10nm) gate dielectric layer；Use again aqueous solution method low temperature prepare high permeability, The In of high mobility2O3Semiconductor channel layer, thus it is prepared as high performance thin film transistor (TFT), Its electric property fully meets the display requirement to thin film transistor (TFT) (TFT).
To achieve these goals, the present invention specifically includes following processing step:
(1), the preparation of precursor solution: by acetylacetone,2,4-pentanedione zirconium Zr (C5H7O2)4It is dissolved in dimethyl In Methanamide, it is simultaneously introduced the ethanolamine with acetylacetone,2,4-pentanedione zirconium equimolar amounts as stabilizer, zirconium Molar content [Zr4+] it is 0.01-0.9；Ethanolamine with the volume ratio of dimethylformamide is 1:1-10；At 20-100 DEG C, the presoma of magnetic agitation 1-24 hour formation clear is molten Liquid, wherein zirconium oxide precursor solution concentration is 0.01-0.5M；
(2), the preparation of film sample: using plasma cleaning method cleans low-resistance silicon substrate Surface, low-resistance silicon substrate after cleaning uses the sol-gel technique spin-coating step of routine (1) precursor solution prepared obtains sample, after spin coating terminates, sample is put into high-pressure mercury Carry out ultraviolet lighting under lamp and process the sample after obtaining photo-annealing, make sample realize photodissociation and solidification Purpose；The sample after photo-annealing is carried out 300 DEG C of process annealings 1-3 hour again, it is to avoid half The interlayer that conductor channel layer process annealing process is brought dissolves each other phenomenon, obtains film sample；
(3)、In2O3The preparation of channel layer: by indium nitrate In (NO3)3It is dissolved in distilled water, It is stirred at room temperature the In that concentration is 0.1-0.3mol/L forming clear for 1-24 hour2O3 Aqueous solution；Then the film sample surface obtained in step (2) utilizes sol-gel technique Use commercially available sol evenning machine spin coating In2O3Aqueous solution, first at 400-600 rev/min of lower spin coating 4-8 Second, then 2000-4000 rev/min of lower spin coating 15-30 second, spin coating number of times is 1-3 time, often Secondary spin coating thickness 5-10nm；Film sample after spin coating is put into 120-150 DEG C burned carry out Put into after cured and Muffle furnace carries out 200-300 DEG C of process annealing process 1-3 hour, system Obtain In2O3Thickness is the In of 5-30nm2O3Thin film, i.e. prepares In2O3Channel layer；
(4), the preparation of source, drain electrode: utilize conventional Vacuum sublimation to utilize rustless steel Mask plate is at In2O3Channel layer source prepared above, drain electrode, i.e. obtain based on ultra-thin ZrOxHigh Aqueous In of k dielectric layer2O3Thin film transistor (TFT).
The plasma clean method related in the step (2) of the present invention uses oxygen or argon to make For purge gas, its power is 20-60Watt, and scavenging period is 20-200s, working gas Intake be 20-50 SCCM；Use sol evenning machine spin coating when preparing film sample, first exist 400-600 rev/min of lower spin coating 4-8 second, then 3000-6000 rev/min of lower spin coating 15-25 second； Spin coating number of times is 1-5 time, and the film thickness of each spin coating is 4-8nm；The merit of high voltage mercury lamp Rate is 1-2KW, and the dominant wavelength of ultraviolet light is 365nm, and light application time is 20-40 minute, High voltage mercury lamp light source distance sample surfaces 5-100cm.
The electrode raceway groove length-width ratio of thin film transistor (TFT) prepared by step of the present invention (4) is 1:4-20, Thermal evaporation electric current is 30-50A；Prepare source, leak electricity extremely metal Al or Au electrode, electricity Pole thickness is 50-200nm.
The present invention compared with prior art, has the advantage that one is partly leading in thin film transistor (TFT) Body channel layer and high k dielectric layer all utilize chemical solution method to prepare, chemical solution system Very cheap, its preparation process need not high vacuum environment, can carry out in atmosphere, reduces Cost；Reaction can be carried out at low temperatures, avoids the appearance of high temperature dephasign while reducing cost； Two is that using plasma cleans substrate surface, attached with substrate of precursor solution when increasing spin coating Put forth effort so that the film sample surface after spin coating is more homogeneous and smooth；Three is to use ultraviolet light The mode that photo-annealing and Low Temperature Thermal annealing combine obtains densification, novel novel grid dielectric material ZrOx, it is to avoid traditional sol-gel film-forming process is for high temperature (> 500 DEG C) demand, make The ZrO that must preparexDielectric layer can be prepared in plastic, for flexible, Transparence Display device Application establish important foundation；Four is prepared ZrOxThe physical thickness of high k gate dielectric layer is only 10nm, it is integrated for device size that the low-leakage current simultaneously having meets microelectronics well Demand；ZrOxHigh permeability that thin film itself has (visible light wave range close to 90%), meets The transparent electronics requirement to material self；The ZrO preparedxThin film is amorphous state, can realize Large area is industrially prepared；Five is that in thin film transistor (TFT), semiconductor channel layer utilizes aqueous solution method Preparation.Use distilled water as solvent phase, than conventional organic solvents, there is nontoxic, environmental protection etc. Advantage；Meanwhile, aqueous solution is less demanding to ambient humidity, therefore reduces being prepared as further This；Finally, due to distilled water does not have corrosivity, when dripping to ZrOxTime on gate dielectric layer, no ZrO can be corrodedxSurface, therefore beneficially forms the interface become apparent from, and this is for TFT device table Existing high-performance electric property is most important；Six is to utilize aqueous solution to prepare In2O3Semiconductor film The high permeability (visible light wave range is more than 80%) that film itself has, meets transparent electronics Requirement；The low temperature that its low temperature (< 300 DEG C) preparation condition requires with flat panel display simultaneously Manufacturing technology is mutually compatible；Its general embodiment low cost, technique is simple, and principle is reliable, produces Moral character can be good, prepares environmental friendliness, has a extensive future, prepare for large area high performance thin Film transistor provides feasible scheme.
Accompanying drawing illustrates:
Fig. 1 be the present invention prepare based on ZrOxAqueous In of high k dielectric layer2O3Film crystal The structural principle schematic diagram of pipe.
Fig. 2 is that the thin film transistor (TFT) prepared of the present invention is at different In2O3Output during annealing temperature Performance diagram, wherein grid bias VGS=1.5V, the In of curve a2O3Annealing temperature is 200 ℃；The In of curve b2O3Annealing temperature is 230 DEG C；The In of curve c2O3Annealing temperature is In2O3-250℃；The In of curve d2O3Annealing temperature is In2O3-270℃。
Fig. 3 is that the thin film transistor (TFT) prepared of the present invention is at different In2O3Transfer during annealing temperature Performance diagram, wherein source-drain voltage VDS=1.0V, the In of curve a2O3Annealing temperature is 200 ℃；The In of curve b2O3Annealing temperature is 230 DEG C；The In of curve c2O3Annealing temperature is In2O3-250℃；The In of curve d2O3Annealing temperature is In2O3-270℃。
Detailed description of the invention:
Below by specific embodiment and combine accompanying drawing and further illustrate the present invention.
Embodiment:
Acetylacetone,2,4-pentanedione zirconium in the present embodiment and indium nitrate powder, dimethylformamide, ethanolamine Organic solvent is all purchased from Aladdin company, and purity is more than 98%；Its bottom grating structure is with ultra-thin oxidation Zirconium (ZrOx) it is high k dielectric layer and with aqueous Indium sesquioxide. (In2O3) thin film is the thin of channel layer The preparation process of film transistor is:
(1) sol-gel technique is first used to prepare ultra-thin ZrOxHigh k dielectric film:
Step 1: select commercially available single-sided polishing low-resistance silicon as substrate (ρ < 0.0015 Ω Cm) and gate electrode, low-resistance silicon substrate is successively by Fluohydric acid., acetone, ethanol ultrasonic waves for cleaning Each 10 minutes of substrate, after repeatedly rinsing with deionized water, high pure nitrogen dries up；
Step 2: dimethylformamide is mixed molten with ethanolamine according to the configuration of mol ratio 2:1 Liquid, is dissolved in acetylacetone,2,4-pentanedione zirconium in this mixed solution according to 0.1M, weighs mixed solution 10mL, Weighing acetylacetone,2,4-pentanedione zirconium is 0.48g, and after mixing, under the effect of magnetic agitation, water-bath 70 DEG C is stirred Mix 3 hours and form clarification, transparent precursor liquid；
Step 3: clean low-resistance silicon substrate is put into plasma clean intracavity, treats that chamber is taken out Taking to 0.5Pa and be passed through high-purity (99.99%) oxygen, controlling its power is 30Watt, Scavenging period is 120s, and during work, the intake of oxygen is 30SCCM；
Step 4: preparation ZrOxSample: the precursor solution of preparation in step 2 is spin-coated on clearly On washed low-resistance silicon substrate, spin coating number of times is 1～5 time, spin coating during spin coating precursor solution The parameter of machine is set to: first 500 revs/min of spin coatings 5 seconds, then 5000 revs/min of spin coatings 25 seconds；After spin coating terminates, sample is put under high voltage mercury lamp and carries out ultraviolet light polymerization process, High voltage mercury lamp power is 1KW, and dominant wavelength is UVC and UVD, and the uv-exposure time is 30 points Clock, mercury lamp light source distance sample surfaces 10cm, by the ZrO after curedxHorse put into by sample Not in stove, process annealing processes, and annealing temperature is 300 DEG C, and annealing time 1 hour obtains ZrOx Sample；
(2) In is utilized2O3In is prepared in aqueous solution spin coating2O3Channel layer:
Step 1: be dissolved in distilled water by indium nitrate powder, indium ion concentration is 0.1M；? In this experiment, weighing distilled water 10mL, weighing indium nitrate is 0.3g, at magnetic force after mixing The In that 12 hour form clear is stirred at room temperature under the effect of stirring2O3Aqueous solution；
Step 2: preparation In2O3Channel layer: by the In of preparation in step 12O3Aqueous solution spin coating At the ZrO processedxOn sample, during spin coating, the parameter of sol evenning machine is set to: first 500 turns/ Distribute equally glue 5 seconds, then 3000 revs/min of spin coatings 25 seconds, after spin coating terminates, sample is put Entering process annealing in Muffle furnace to process, annealing temperature is respectively 200,230,250,270 DEG C, annealing time 1 hour；
(3) Vacuum sublimation is used to prepare source, leak metal electrode:
By the way of thermal evaporation, at In2O3It is 1000/100 μm by breadth length ratio on channel layer Rustless steel mask plate prepare metal Al thick for 100nm as source, drain electrode, thermal evaporation Electric current is 40A, prepares Al/In2O3/ZrOxThe thin film transistor (TFT) of/Si structure；
(4) to the Al/In made2O3/ZrOxThe thin film transistor (TFT) of/Si structure (Fig. 1) is carried out Test；At different In2O3Thin film transistor (TFT) output characteristic curve under annealing temperature condition utilizes The test of Keithley 2634B semiconductor source table obtains (Fig. 2)；The thin film transistor (TFT) pair of preparation The transfer characteristic curve (Fig. 3) answered is surveyed also with Keithley 2634B semiconductor source table Examination obtains, wherein with the In of 200,230,250,270 DEG C of annealings2O3For channel layer TFT Transfer characteristic curve respectively corresponding diagram 3 in a, b, c, d.

Claims (3)

1. a preparation method for high k dielectric layer aqueous indium oxide film transistor, its feature It is to specifically include following processing step:
(1), the preparation of precursor solution: by acetylacetone,2,4-pentanedione zirconium Zr (C5H7O2)4It is dissolved in dimethyl In Methanamide, it is simultaneously introduced ethanolamine with acetylacetone,2,4-pentanedione zirconium equimolar amounts as stabilizer, At 20-100 DEG C, magnetic agitation 1-24 hour forms the precursor solution of clear, wherein oxygen Changing zirconium precursor liquid solution concentration is 0.01-0.5M, zirconium Zr4+Molar content be 0.01-0.9； Ethanolamine is 1:(1-10 with the volume ratio of dimethylformamide)；
(2), the preparation of film sample: using plasma cleaning method cleans low-resistance silicon substrate Surface, low-resistance silicon substrate after cleaning uses the sol-gel technique spin-coating step of routine (1) precursor solution prepared obtains sample, after spin coating terminates, sample is put into high-pressure mercury Carry out ultraviolet lighting under lamp and process the sample after obtaining photo-annealing, it is achieved the photodissociation of sample is with solid Change；The sample after photo-annealing is carried out 300 DEG C of process annealings 1-3 hour again, it is to avoid quasiconductor The interlayer that channel layer process annealing process is brought dissolves each other phenomenon, obtains ZrOxFilm sample；
(3)、In2O3The preparation of channel layer: by indium nitrate In (NO3)3It is dissolved in distilled water, It is stirred at room temperature the In that concentration is 0.1-0.3mol/L forming clear for 1-24 hour2O3 Aqueous solution；Then the ZrO obtained in step (2)xFilm sample surface utilizes sol-gel Technology uses commercially available sol evenning machine spin coating In2O3Aqueous solution, the evenest under 400-600 rev/min The glue 4-8 second, then 2000-4000 rev/min of lower spin coating 15-30 second, spin coating number of times is 1-3 Secondary, each spin coating thickness 5-10nm；By the ZrO after spin coatingxFilm sample is put into 120-150 DEG C Burned carry out cured after put into and Muffle furnace carries out 200-300 DEG C of process annealing process 1-3 hour, prepare In2O3Thickness is the In of 5-30nm2O3Thin film, i.e. prepares In2O3 Channel layer；
(4), the preparation of source, drain electrode: utilize conventional Vacuum sublimation to utilize rustless steel Mask plate is at In2O3Channel layer source prepared above, drain electrode, i.e. obtain based on ZrOxHigh k is situated between Aqueous In of electric layer2O3Thin film transistor (TFT).
High k dielectric layer aqueous indium oxide film transistor the most according to claim 1 Preparation method, it is characterised in that the plasma clean method related in step (2) uses oxygen Or argon is as purge gas, its power is 20-60Watt, and scavenging period is 20-200s, The intake of working gas is 20-50SCCM；Sol evenning machine spin coating is used when preparing film sample, First 400-600 rev/min of lower spin coating 4-8 second, then at 3000-6000 rev/min of lower spin coating 15-25 Second；Spin coating number of times is 1-5 time, and the film thickness of each spin coating is 4-8nm；High voltage mercury lamp Power be 1-2KW, the dominant wavelength of ultraviolet light is 365nm, and light application time is that 20-40 divides Clock, high voltage mercury lamp light source distance sample surfaces 5-100cm.
High k dielectric layer aqueous indium oxide film transistor the most according to claim 1 Preparation method, it is characterised in that the electrode raceway groove length and width of thin film transistor (TFT) prepared by step (4) Ratio is 1:(4-20), thermal evaporation electric current is 30-50A；Prepare source, leak electricity extremely metal Al or Au electrode, thickness of electrode is 50-200nm.
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