CN103956325B - The preparation method of a kind of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor - Google Patents
The preparation method of a kind of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 239000010408 film Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004065 semiconductor Substances 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 238000001659 ion-beam spectroscopy Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000005516 engineering process Methods 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 20
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 238000000231 atomic layer deposition Methods 0.000 claims description 16
- 238000004544 sputter deposition Methods 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000002207 thermal evaporation Methods 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 230000002708 enhancing effect Effects 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010884 ion-beam technique Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002064 alloy oxide Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910005224 Ga2O Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000002000 scavenging effect Effects 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 239000003989 dielectric material Substances 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 description 3
- 238000003877 atomic layer epitaxy Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910007541 Zn O Inorganic materials 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OPCPDIFRZGJVCE-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Zn+2].[In+3].[Ti+4] OPCPDIFRZGJVCE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/66742—Thin film unipolar transistors
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28229—Making the insulator by deposition of a layer, e.g. metal, metal compound or poysilicon, followed by transformation thereof into an insulating layer
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Ceramic Engineering (AREA)
- Thin Film Transistor (AREA)
Abstract
The invention belongs to semiconductor material thin film transistor preparing technical field, it relates to the preparation method of a kind of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor, first grow GTO MULTILAYER COMPOSITE sull and obtain laminated film sample; Again laminated film sample is annealed the preparation of GTO high K medium dielectric layer, obtained the film sample containing GTO dielectric layer; Then the film sample containing GTO dielectric layer is put into the surface of the indoor cleaning film sample of ion beam sputtering, the film sample after being cleaned; Again the GTO dielectric layer of film sample after cleaning deposits ITZO semiconductor channel layer, obtain channel layer thin film sample; On channel layer thin film sample, finally prepare source, leakage metal electrode, obtain the ITZO thin film transistor of MULTILAYER COMPOSITE oxide compound GTO high k dielectric layer; Its technique is simple, and principle is reliable, and cost is low, good product performance, and preparation environmental friendliness, application prospect is good.
Description
Technical field:
The invention belongs to semiconductor material thin film transistor preparing technical field, relate to a kind of MULTILAYER COMPOSITE oxide compound (GTO) high k dielectric and novel semi-conductor channel material indium titanium zinc oxide (In-Ti-Zn-O, ITZO) preparation technology of quad alloy sull, the particularly preparation method of a kind of MULTILAYER COMPOSITE oxide compound GTO high K medium thin film transistor.
Background technology:
In recent years, thin film transistor (ThinFilmTransistor, TFT) at driven with active matrix liquid crystal display device (ActiveMatrixLiquidCrystalDisplay, AMLCD) vital role has been played in, more and more ripe from low temperature amorphous silicon TFT to the technology of high temperature polysilicon TFT, application also not only can drive LCD but also can drive OLED (OrganicLightEmittingDiodes) and Electronic Paper from LCD (LiquidCrystalDisplay) can only be driven to develop into. Along with semiconductor process technology improves constantly, Pixel Dimensions constantly reduces, the resolving power 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 materials energy gap determines the size of leakage current, and its relative permittivity then determines the size (i.e. energy consumption size) of device subthreshold swing. Along with the development of large-scale integrated circuit, the characteristic dimension as the MOS (metal-oxide-semiconductor) transistor of si-substrate integrated circuit core devices constantly reduces always, and it reduces rule and follows Moore's Law. At present lithographic dimensioned has reached 28nm, CMOS gate equivalent oxide thickness drops to below 1nm, the thickness of gate oxide is close to interatomic distance (IEEEElectronDeviceLett.2004,25 (6): 408-410), along with the reduction of equivalent oxide thickness can cause tunnel effect; Research shows SiO2Thickness when reducing to 1.5nm by 3.5nm grid leakage current by 10-12A/cm2Increase to 10A/cm2(IEEEElectronDeviceLett.1997,18 (5): 209-211), bigger leakage current can cause high power consumption and corresponding heat dissipation problem, this all causes disadvantageous impact for device integration, reliability and life-span, is therefore badly in need of the high dielectric material replacement traditional Si O that research and development make new advances2. At present, extensively adopt in MOS integrated circuit technology high-k (high k) gate medium to increase capacitance density and reduce grid leakage current, high-g value because of its big specific inductivity, with SiO2When having same equivalent gate oxide thickness (EOT), its actual (real) thickness compares SiO2Big many, thus solve SiO2Because of the problem produced close to the physical thickness limit.
The existing novel high-k dielectric material becoming research focus comprises Al2O3(ElectronicalandSolid-StateLetters, 12, H123,2009), Y2O3(AppliedSurfaceScience.256,2245,2010),��ZrO2(AppliedPhysicsLetters,99,232101,2011),��Sc2O3(AppliedPhysicsLetters,101,232109,2012)��HfO2(JournalofAppliedPhysics, 107,014104,2010) and Ta2O5(IEEEElectronDeviceLetters, 31,1245,2010) etc.; TFT device is film-type structure, and the specific inductivity of its gate dielectric layer, surfaceness, compactness extent are very big to the electric property of TFT. By consulting existing related article, patent, not yet find to utilize the Atomic layer deposition method of plasma enhancing to prepare Ga2O3,TiO2MULTILAYER COMPOSITE oxide compound (GTO) is as the relevant report of thin film transistor grid dielectric materials. In GTO composite oxides, Ga2O3And TiO2As two kinds of wide bandgap semiconductor (Ga2O3Energy gap be 4.8eV, TiO2Energy gap be 3.2eV), there is the big (Ga of relative permittivity2O3Specific inductivity is 10-14, TiO2Specific inductivity is 80-160) etc. advantage, its composite structure will be a kind of desirable high-k dielectric material. Utilizing GTO film prepared by the technique for atomic layer deposition of plasma enhancing as the novel high-k dielectric material of one, its energy gap is 4.0eV, and relative permittivity reaches 30 (much larger than SiO2Own specific inductivity 9). In addition, GTO film has very high thermostability and disruptive field intensity, and Sauerstoffatom has very strong blocking capability, and therefore, the GTO height K thin film utilizing the technique for atomic layer deposition of plasma enhancing to prepare is suitable as the gate dielectric layer of thin film transistor very much.
Ald (AtomicLayerDeposition of the prior art, ALD), it is called atomic layer epitaxy (AtomicLayerEpitaxy at first, ALE), also referred to as atomic layer chemical vapor deposition (AtomicLayerChemicalVaporDeposition, ALCVD). Technique for atomic layer deposition is adopted to prepare film due to the deposition uniformity of its excellence and consistence, deposition parameter is such as thickness, the high controllability of structure, make it have a wide range of applications potentiality in fields such as micro-nano electronics and nano materials, therefore adopt ald preparation technology can prepare the GTO high K medium film of high quality and accurate thickness. But the general temperature requirement utilizing ALD technique deposit film reaches more than 500 DEG C, and the ald of plasma enhancing (Plasma-EnhancedAtomicLayerDeposition, PE-ALD) by the enhancement of plasma, film deposition temperature can be made greatly to reduce, even at room temperature just can film forming. As the technology of preparing of a kind of semiconductor channel layer, rf magnetron sputtering (Radio-FrequencyMagnetronSputtering) has that sedimentation velocity is fast, base material temperature rise is low, the damage of rete is little; Sputtering technology favorable repeatability, it is possible to obtain the uniform film of thickness on large area substrates; Different metal, alloy, oxide compound can mix, the first-class advantage of substrate can be sputtered at simultaneously, industrially it is widely used, utilizes radiofrequency magnetron sputtering technology to prepare reliability height and the good new multicomponent semiconductor channel layer of repeatability becomes the technology contents that industry inquiring into.
At present, the Synthesis and applications technology of amorphous oxides indium gallium zinc oxygen (IGZO) thin film transistor has open source literature, and big quantity research has done in various countries of Japan and Korea S., in indium-zinc oxide (In-Zn-O, IZO) system, doped gallium (Ga) is being formed thus solve the problem that carrier concentration is too high in order to unbound electron too much in inhibition system and Lacking oxygen. consider and the binding ability of titanium atom (Ti) and oxygen it is higher than the binding ability of Ga atom and oxygen (titanium atom has lower Standard Electrode Potentials compared to gallium atom, ChinesePhysicsLetters, 30, 127301, 2013), can predict that the IZO system mixing Ti has the effect OFF state power consumption size of thin film transistor (concentration of current carrier be directly connected to) better suppressing carrier concentration in theory, so a kind of novel quad alloy indium titanium zinc oxide (ITZO) will become a kind of transparent amorphous oxide system having very much researching value, it is that the thin film transistor of channel layer overcomes the lower carrier mobility of non-crystalline silicon tft (generally at 0.1-1.0cm taking ITZO2��V-1��s-1In scope) problem, such that it is able to accomplish high speed, high brightness, high-contrast display screen information, ITZO film has the feature (being greater than 80% in visible light wave range transmitance) of high-clarity in addition, its TFT is as the pixel switch of AMLCD, to greatly improve the opening rate of active matrix, it is to increase while brightness, reduce power consumption. Adopt magnetron sputtering technique can realize large area film deposition, compare tradition non-crystalline silicon and there is higher electronic mobility and homogeneity, utilizing low-temperature annealing technology to make its cost of manufacture cheaper in addition, these character make its transparent electron display device field in future have very wide potential market.
Summary of the invention:
It is an object of the invention to overcome the shortcoming of prior art existence, seek to design and provide the preparation method of a kind of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor, adopt the atomic layer deposition sum short annealing technology of plasma enhancing to prepare GTO (Ga2O3��TiO2) MULTILAYER COMPOSITE oxide compound is as high K medium; At room temperature adopt radio frequency magnetron sputtering method prepare high permeability, high mobility novel I TZO quad alloy semiconductor film as channel layer.
In order to realize above-mentioned purpose, the technical scheme of the present invention comprises following processing step:
(1), the preparation of GTO high K medium dielectric layer: adopt purity to be the [(CH of 100%3)2GaNH2]3With the Ti [N (CH that purity is 100%3)2]4Respectively as Ga2O3And TiO2Presoma; With the technique for atomic layer deposition growth GTO MULTILAYER COMPOSITE sull of plasma enhancing at room temperature to 600 DEG C, the physical thickness of every layer is 20-40nm; Ga2O3And TiO2Film is preparation alternately, and total number of plies is 2-20 layer, obtains laminated film sample; By the laminated film sample of preparation in high-purity N2In atmosphere, control temperature is 200-600 DEG C of annealing 8-12 minute, completes the preparation of GTO high K medium dielectric layer, obtains the film sample containing GTO dielectric layer;
(2), the surface cleaning of film sample: the film sample containing GTO dielectric layer is put into ion beam sputtering indoor, adopts ion beam sputtering technology to utilize the Ar ionized out+Clean the surface of film sample, remove surface contaminant; In cleaning process, argon flow amount is 2-6SCCM; Cleaning device operating air pressure is 4 �� 10-2Pa; Line is 5-20mA; Scavenging period is 50-70 second, completes the surface cleaning of film sample, the film sample after being cleaned;
(3), the preparation of ITZO semiconductor channel layer: utilize conventional radiofrequency magnetron sputtering technology, adopt ZnO and TiO2Alloys target and In2O3The mode of the double target co-sputtering of target, on the GTO dielectric layer of film sample after cleaning, room temperature deposition thickness is the ITZO semiconductor channel layer of 20-200nm, obtains channel layer thin film sample; Wherein oxide target material powder purity is all higher than 99.99%;
(4), the preparation of source, leakage metal electrode: utilize conventional vacuum thermal evaporation to prepare source, leakage metal electrode on channel layer thin film sample, namely the ITZO thin film transistor of MULTILAYER COMPOSITE oxide compound GTO high k dielectric layer is obtained, its threshold voltage is 0.19V, subthreshold swing is 64mV/dec, and current on/off ratio is less than 2 �� 105, high comprehensive performance.
During employing ald (PE-ALD) the deposition techniques GTO high K medium dielectric layer that step of the present invention (1) relates to, select heavily doped P-type silicon 100 as substrate, acetone and the purity alcohol ultrasonic cleaning that is greater than 99.0% of 99.0% it is greater than successively by purity, then repeatedly rinsing with deionized water, nitrogen blows puts into deposition (PE-ALD) reaction chamber by silicon substrate after doing; Recycling ald (PE-ALD) deposition techniques GTO high K medium dielectric layer, adopts purity to be the [(CH of 100% respectively3)2GaNH2]3With the Ti [N (CH that purity is 100%3)2]4As Ga2O3And TiO2Presoma, rare gas element Ar as the carrier gas transporting reaction source, oxygen as reaction gas, under the effect of plasma body, Ga2O3And TiO2Presoma and oxygen generation chemical reaction generate Ga2O3And TiO2, its depositing temperature is room temperature to 600 DEG C, and deposition (PE-ALD) reaction chamber pressure is 0.1-1Torr; Ga2O3And TiO2By layer growth, deposition (PE-ALD) technology is utilized first to deposit 8-12 unimolecular layer Ga on a silicon substrate2O3Film, then at Ga2O3Film continues deposition 8-12 unimolecular layer TiO2Film, replaces 2-20 time successively, forms the laminated film sample of 2-20 layer; Deposit one layer of Ga2O or TiO2The reaction time of film comprises: the time of the inertia current-carrying gas removal resistates of the gallium source of 0.1-10 second or titanium source gas pulses time, the inertia current-carrying gas removal residue time of 2-50 second, the oxygen gas plasma burst length of 0.1-10 second and 2-50 second.
It is the medium layer surface utilizing ion beam cleaning rifle to clean film sample that employing ion beam sputtering technology described in step of the present invention (2) cleans film sample surface, first the film sample containing GTO dielectric layer being put into ion beam sputtering chamber interior, being extracted into vacuum pressure is 3 �� 10-4Leading to into argon gas after Pa, heater current adds to 4A to tungsten filament preheating, and preheating carries out pre-sputtering after completing, and its beam intensity is 8-12mA, and sparking voltage is 60-80V, and operating air pressure is 4 �� 10-2Pa; Film sample shifting to target position is carried out cleaning medium layer surface after completing by pre-sputtering, is cleaned 50-60 second by GTO film surface, effectively removing film sample surface contaminant under ensureing the experiment condition of pre-sputtering.
Material ITZO (the In of the semiconductor channel layer described in step of the present invention (3)2O3,TiO2, ZnO) and the conventional radiofrequency magnetron sputtering technology room temperature preparation of quad alloy oxide compound, regulate different atom ratio in film sample, control channel layer ITZO carrier concentration by changing sputtering power; Or by regulating argon gas, oxygen pneumatic than the resistivity and the carrier concentration that regulate ITZO film.
The vacuum thermal evaporation related in step of the present invention (4) utilizes stainless steel mask to prepare source-drain electrode, and electrode raceway groove long-width ratio is 1:4-1:20; Thermal evaporation electric current is 30-50A; Obtained source, leak electricity very metallic aluminium, gold, nickel electrode, thickness of electrode is 50-200nm.
The present invention is compared with prior art, have the following advantages: one is that thin film transistor dielectric layer completes in atomic layer deposition apparatus, the relative physics filming equipment of technique for atomic layer deposition has excellent deposition uniformity and consistence, deposition parameter such as thickness, the high controllability of structure; Relative to other chemical processes, technique for atomic layer deposition has film densification, film forming one after another advantages of higher; Two is adopt high-purity [(CH3)2GaNH2]3With Ti [N (CH3)2]4As Ga2O3And TiO2Starting material presoma, by the control deposition number of plies can effective control grid thickness of dielectric layers, what meet large-scale integrated circuit develops the requirement to accurate control device size; The multilayer materials GTO that three is obtained belongs to novel high-k dielectric material (having no report), and energy gap is 4.0eV, and specific inductivity reaches 30 (much larger than SiO2Specific inductivity 9 own), its high dielectric characteristics meets the requirement of modern technique of display for high-g value completely; And the high permeability that GTO film has itself (visible light wave range is greater than 80%) meets the requirement of transparent electronics; Four is that GTO film is in high-purity N2In atmosphere, short annealing process, is avoiding SiO2While producing, it is to increase the compactness of GTO grid dielectric materials and electrical properties; Five is that growth has the sample of GTO put into indoor, ion beam sputtering chamber, and we utilize ion beam cleaning rifle " cleaning " GTO sample surfaces, avoid the interface pollution thing between GTO dielectric layer and semiconductor channel layer to the deterioration of TFT device property; Six is that in thin film transistor, semiconductor channel layer completes in rf magnetron sputtering equipment, and magnetron sputtering technique has that sedimentation velocity is fast, base material temperature rise is low, the damage of rete is little; Sputtering technology favorable repeatability, it is possible to obtain the uniform film of thickness on large area substrates; Different metal, alloy, oxide compound can carry out mixing and cosputtering is to the first-class advantage of substrate simultaneously; Seven be with magnetically controlled sputter method deposition alloy semiconductor layer be a kind of novel quad alloy oxide compound (ITZO), adopt ZTO target material (ZnO, TiO2Alloys target purity is 99.99%) and In2O3The mode of (purity is 99.99%) target material cosputtering; The extremely high transmitance (visible light wave range is greater than 80%) that ITZO film has itself, meets the requirement of transparent electronics; The low temperature manufacturing technology that room temperature preparation condition and flat panel display require is mutually compatible; Quad alloy amorphous oxide thin film technology is conducive to improving thin film stability in addition, thus improves TFT device stability; Its general embodiment cost is low, and technique is simple, and principle is reliable, good product performance, and preparation environmental friendliness, application prospect is good, it may be achieved big area prepares high performance thin film transistor.
Accompanying drawing illustrates:
Fig. 1 is the structural principle schematic diagram of the GTO film that the present invention is prepared on substrate.
Fig. 2 is the structural principle schematic diagram of GTO composite oxide film transistor prepared by the present invention.
Fig. 3 is the output characteristic curve of thin film transistor prepared by the present invention, and wherein a is VGS=0V; B is VGS=10V; C is VGS=20V; D is VGS=30V.
Fig. 4 is the transfer characteristic curve of thin film transistor prepared by the present invention, and wherein a is subthreshold swing=64mV/dec; B is threshold voltage=0.19V.
Fig. 5 is the semiconductor channel layer InTiZnO film that the present invention relates to transmittance curve at visible light wave range.
Fig. 6 is X-ray diffraction (XRD) collection of illustrative plates of the semiconductor channel layer InTiZnO film that the present invention relates to, and ITZO film is noncrystalline state.
Embodiment:
Below by specific embodiment and the present invention is described by reference to the accompanying drawings further.
Embodiment 1:
The present embodiment prepares the MULTILAYER COMPOSITE oxide compound GTO high K medium thin film transistor of a kind of bottom grating structure, and its concrete preparation process is:
(1) technique for atomic layer deposition is adopted to prepare GTO high K medium film, see Fig. 1:
Step 1: select P-type silicon 100 as substrate, successively with each 5 minutes of acetone, alcohol ultrasonic cleaning substrate, after repeatedly rinsing with deionized water, high pure nitrogen blows dry, obtains clean substrate;
Step 2: preparation GTO high k dielectric layer: the substrate of cleaning is put into PE-ALD reaction chamber immediately, is 200 DEG C in temperature, when reaction chamber pressure is 0.1Torr, with Ti [N (CH3)2]4As the presoma of titanium, [(CH3)2GaNH2]3As the presoma of gallium, oxygen is as the reaction gas of plasma oxygen, and argon gas, as current-carrying gas, adopts PE-ALD technology to grow the GTO medium layer of 36nm on P type (100) silicon substrate; The deposit of GTO is based on [(CH3)2GaNH2]3��Ti[N(CH3)2]4And the chemical reaction between oxygen:
Ti[N(CH3)2]4+O2��TiO2+ resultant
[(CH3)2GaNH2]3+O2��Ga2O3+ resultant
When forming GTO high-k dielectric layer, unimolecular layer number of deposition cycles elects 100 times as; The reaction time of a deposition GTO comprises: Ti [N (CH3)2]4Or [(CH3)2GaNH2]3Burst length t1It it is 1 second; It is t that argon gas removes the entrap bubble time2=50 seconds; The oxygen gas plasma burst length is t3=1 second; It is t that argon gas removes the time of residual oxygen and reflection resultant4=50 seconds; The time needed for reaction of a deposition GTO is T=t1+t2+t3+t4=102 seconds;
Step 3: in high-purity N2Under atmosphere, GTO film sample being carried out short annealing process, annealing temperature is 500 DEG C, and heat-up rate often divides 30 DEG C, and annealing time is 10 minutes;
(2) ion beam cleaning rifle cleans dielectric layer surface:
Step 1: pre-sputtering, puts into ion beam chamber inside by GTO sample, high vacuum (3 �� 10 to be extracted into-4Pa) leading to afterwards into 4SCCM argon gas, heater current adds to 4A, and sparking voltage is 70V, preheating 5 minutes, pre-sputtering 10 minutes after preheating completes, and now beam intensity is 10mA, and sparking voltage is 70V, and operating air pressure is 4 �� 10-2Pa;
Step 2: clean GTO dielectric layer, moves sample and tests to corresponding target position, under ensureing the experiment condition of pre-sputtering, GTO film surface is cleaned 1 minute;
Step 3: in high vacuum (3 �� 10 after to be cleaned-4Pa) under, sample is directly transported to the indoor specimen holder in magnetron sputtering chamber from ion beam chamber, effectively avoids the detrimentally affect that impurity in air drops down onto interface and causes;
(3) ITZO channel layer is prepared: select ITZO channel layer growth parameter(s): background air pressure is 1-2 �� 10-4Pa; Target group part is ZnO+TiO2Alloys target and In2O3Target, ZnO and TiO2Purity be 99.99%, In2O3Purity be 99.99%; Sputtering power is ZTO=70W, In2O3=50W; Sputter gas is Ar flow is 60SCCM, O2Flow is 2.5SCCM; Growth air pressure is 1Pa; Growth temperature is room temperature; Growth time is 20min; Film thickness is 120nm;
(4) method of vacuum thermal evaporation is adopted to prepare source, leakage metal electrode: by the mode of thermal evaporation, the stainless steel mask being 1000/100 ��m by breadth-length ratio above ITZO channel layer prepares the thick metallic nickel electrode of 100nm, and thermal evaporation electric current is 50A;
(5) thin film transistor by the Ni/ITZO/GTO/Si structure (Fig. 2) made is tested; Being undertaken testing (Keithley2612A) by the InTiZnO thin film transistor TFT device made, output, transfer characteristic curve are tested as shown in Figure 3,4; ITZO film utilizes Shimadzu UV-2550 test to obtain at the transmittance curve (Fig. 5) of visible ray; The crystallization degree of ITZO film is as shown in Figure 6.
Claims (5)
1. the preparation method of a MULTILAYER COMPOSITE oxide compound high K medium thin film transistor, it is characterised in that comprise following processing step:
(1) preparation of GTO high K medium dielectric layer: adopt purity to be the [(CH of 100%3)2GaNH2]3With the Ti [N (CH that purity is 100%3)2]4Respectively as Ga2O3And TiO2Presoma; With the technique for atomic layer deposition growth GTO MULTILAYER COMPOSITE sull of plasma enhancing under room temperature to 600 DEG C temperature condition, the physical thickness of every layer film is 20-40nm; Ga2O3And TiO2Film is preparation alternately, and total number of plies is 2-20 layer, obtains laminated film sample; By the laminated film sample of preparation in high-purity N2In atmosphere, control temperature is 200-600 DEG C of annealing 8-12 minute, completes the preparation of GTO high K medium dielectric layer, obtains the film sample containing GTO dielectric layer;
(2) surface cleaning of film sample: the film sample containing GTO dielectric layer is put into ion beam sputtering indoor, adopts ion beam sputtering technology to utilize the Ar ionized out+Clean the surface of film sample, remove surface contaminant; In cleaning process, argon flow amount is 2-6SCCM; Cleaning device operating air pressure is 4 �� 10-2Pa; Line is 5-20mA; Scavenging period is 50-70 second, completes the surface cleaning of film sample, the film sample after being cleaned;
(3) preparation of ITZO semiconductor channel layer: utilize radiofrequency magnetron sputtering technology, adopts ZnO and TiO2Alloys target and In2O3The mode of the double target co-sputtering of target, on the GTO dielectric layer of film sample after cleaning, room temperature deposition thickness is the ITZO semiconductor channel layer of 20-200nm, obtains channel layer thin film sample; Wherein oxide target material powder purity is all higher than 99.99%;
(4) preparation of source, leakage metal electrode: utilize vacuum thermal evaporation preparation source, leakage metal electrode on channel layer thin film sample, namely the ITZO thin film transistor of MULTILAYER COMPOSITE oxide compound GTO high k dielectric layer is obtained, its threshold voltage is 0.19V, subthreshold swing is 64mV/dec, and current on/off ratio is less than 2 �� 105��
2. the preparation method of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor according to claim 1, when it is characterized in that the employing technique for atomic layer deposition deposition GTO high K medium dielectric layer that step (1) relates to, select heavily doped P-type silicon 100 as substrate, acetone and the purity alcohol ultrasonic cleaning that is greater than 99.0% of 99.0% it is greater than successively by purity, then repeatedly rinsing with deionized water, nitrogen blows after doing puts into cvd reactive chamber by silicon substrate; Recycling technique for atomic layer deposition deposition GTO high K medium dielectric layer, adopts purity to be the [(CH of 100% respectively3)2GaNH2]3With the Ti [N (CH that purity is 100%3)2]4As Ga2O3And TiO2Presoma, rare gas element Ar as the carrier gas transporting reaction source, oxygen as reaction gas, under the effect of plasma body, Ga2O3And TiO2Presoma and oxygen generation chemical reaction generate Ga2O3And TiO2, its depositing temperature is room temperature to 600 DEG C, and cvd reactive chamber pressure is 0.1-1Torr; Ga2O3And TiO2By layer growth, deposition technique is utilized first to deposit 8-12 unimolecular layer Ga on a silicon substrate2O3Film, then at Ga2O3Film continues deposition 8-12 unimolecular layer TiO2Film, replaces 2-20 time successively, forms the laminated film sample of 2-20 layer; Deposit one layer of Ga2O or TiO2The reaction time of film comprises: the time of the inertia current-carrying gas removal resistates of the gallium source of 0.1-10 second or titanium source gas pulses time, the inertia current-carrying gas removal residue time of 2-50 second, the oxygen gas plasma burst length of 0.1-10 second and 2-50 second.
3. the preparation method of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor according to claim 1, it is characterized in that the employing ion beam sputtering technology described in step (2) cleans film sample surface is the medium layer surface utilizing ion beam cleaning rifle to clean film sample, first the film sample containing GTO dielectric layer being put into ion beam sputtering chamber interior, being extracted into vacuum pressure is 3 �� 10-4Leading to into argon gas after Pa, heater current adds to 4A to tungsten filament preheating, and preheating carries out pre-sputtering after completing, and its beam intensity is 8-12mA, and sparking voltage is 60-80V, and operating air pressure is 4 �� 10-2Pa; Film sample shifting to target position is carried out cleaning medium layer surface after completing by pre-sputtering, is cleaned 50-60 second by GTO film surface, effectively removing film sample surface contaminant under ensureing the experiment condition of pre-sputtering.
4. the preparation method of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor according to claim 1, it is characterised in that the material ITZO quad alloy oxide compound of the semiconductor channel layer described in step (3) adopts In2O3��TiO2With ZnO radiofrequency magnetron sputtering technology room temperature preparation, regulate different atom ratio in film sample, control channel layer ITZO carrier concentration by changing sputtering power; Or by regulating argon gas, oxygen pneumatic than the resistivity and the carrier concentration that regulate ITZO film.
5. the preparation method of MULTILAYER COMPOSITE oxide compound high K medium thin film transistor according to claim 1, it is characterized in that the vacuum thermal evaporation related in step (4) utilizes stainless steel mask to prepare source-drain electrode, electrode raceway groove long-width ratio is 1:4-1:20; Thermal evaporation electric current is 30-50A; Obtained source, leak electricity very metallic aluminium, gold, nickel electrode, thickness of electrode is 50-200nm.
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